JP2013226784A - Laminate, method for manufacturing the same, and method for manufacturing device structure body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is composed of a polyimide film and a support, has high heat resistance, is free from peeling in a process where a device is formed on the polyimide film, and in which the polyimide film can be easily peeled off from the support after the device is formed.SOLUTION: In a method for manufacturing a laminate composed of a support and a polyimide film, a coupling agent layer is formed by applying a coupling agent on a surface of the support facing the polyimide film, and then pressurizing and heating treatment is performed while superposing the support and the polyimide film in which a predetermined pattern composed of regions having different amounts of the coupling agent is formed when the coupling agent layer is formed.

Description

  The present invention is a laminate of a polyimide film and a support such as an inorganic substrate, and a laminate capable of easily separating the polyimide film from the support as necessary, a method for producing the laminate, and a device using the laminate The present invention relates to a structure manufacturing method.

  Functional elements (devices) such as semiconductor elements, MEMS elements, and display elements are used as electronic components in information communication equipment (broadcast equipment, mobile radio, portable communication equipment, etc.), radar, high-speed information processing devices, etc. Conventionally, it has been generally mounted on a ceramic substrate. However, in recent years, as electronic parts have been reduced in weight, size, thickness, and flexibility, attempts have been made to form various functional elements on polymer films in place of ceramic substrates that lack flexibility and are difficult to thin. Has been made.

  In forming various functional elements on the surface of the polymer film, it is ideal to process by a so-called roll-to-roll process using the flexibility that is a characteristic of the polymer film. However, in the industries such as the semiconductor industry, the MEMS industry, and the display industry, a process technology for a rigid flat substrate such as a wafer base or a glass substrate base has been mainstream. Therefore, in order to form various functional elements on the surface of the polymer film using the existing infrastructure, the polymer film is bonded to a rigid support made of an inorganic material (glass plate, ceramic plate, silicon wafer, metal plate, etc.). In addition, it is desired to separate from the support after forming the desired element.

  By the way, in a process of forming a desired functional element on a laminate in which a polymer film and an inorganic support are bonded together, the laminate is often exposed to high temperatures. For example, in the formation of functional elements such as polysilicon and oxide semiconductor, a process in a temperature range of about 200 to 500 ° C. is required, and in the production of a low-temperature polysilicon thin film transistor, about 450 ° C. is used for dehydrogenation. When the hydrogenated amorphous silicon thin film is manufactured, a temperature of about 200 to 300 ° C. may be applied to the film. Accordingly, the polymer film constituting the laminate is required to have heat resistance. In addition, it is generally considered to use a pressure-sensitive adhesive or an adhesive for laminating the polymer film to the support, but the bonding surface of the polymer film and the support at that time (that is, an adhesive for laminating or the like) The adhesive also requires heat resistance. However, since a normal bonding adhesive or pressure-sensitive adhesive does not have sufficient heat resistance, bonding with an adhesive or pressure-sensitive adhesive cannot be applied when the functional element formation temperature is high.

  In view of such circumstances, as a laminate of a polymer film and a support for forming a functional element, a polyimide film that has excellent heat resistance and is strong and can be thinned from an inorganic substance via a silane coupling agent. The laminated body bonded together to the support body (inorganic layer) which becomes is proposed (patent documents 1-3).

JP 2010-283262 A JP 2011-11455 A JP 2011-245675 A

  However, in the laminates described in Patent Documents 1 to 3, since the polyimide film and the support are uniformly attached with the same adhesive force, heat and stress when forming a functional element (device) If the adhesive strength is set to be high so as not to peel off, it becomes difficult to separate the film from the support after forming the device, and conversely, if the adhesive strength is set to be weak so that the film after device formation can be easily separated from the support. In some cases, it could not withstand the load of heat and stress during device formation and peeled off.

  The present invention has been made paying attention to the above circumstances, and its purpose is a laminate of a polyimide film and a support, which has high heat resistance and forms a device on the polyimide film. To provide a laminate capable of easily separating a polyimide film from a support after forming a device and a method for producing the laminate, and a method for producing a device structure using the laminate It is.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a coupling agent layer composed of regions having different amounts of coupling agent when laminating a support and a polyimide film via a coupling agent layer. If it has a predetermined pattern, a coupling agent is present only in a small amount or not at all while exhibiting a sufficient adhesive force that does not cause peeling at the time of device formation in an area where a large amount of coupling agent is present. It discovered that the polyimide film which mounted the device could be easily isolate | separated from a support body by notching and peeling to a polyimide film in the area | region, and completed this invention.

That is, the present invention has the following configuration.
1) A method for producing a laminate of a support and a polyimide film, wherein a coupling agent is applied to the surface of the support facing the polyimide film to form a coupling agent layer The support and the polyimide film are overlapped and subjected to pressure and heat treatment, and when forming the coupling agent layer, a predetermined pattern composed of regions having different amounts of coupling agent is formed. A method for manufacturing a laminate.
2) The manufacturing method of the laminated body as described in said 1) using the film which gave the plasma process previously as said polyimide film.
3) The manufacturing method of the laminated body as described in said 2) using the film which gave the acid treatment after the said plasma treatment as said polyimide film.
4) Any one of the above 1) to 3), wherein the coupling agent is applied by at least one selected from the group consisting of inkjet printing, gravure printing, screen printing, planographic printing, reversal printing, microcontact printing, and dispenser coating. The manufacturing method of the laminated body of crab.
5) The method for producing a laminate according to any one of 1) to 4), wherein the pressure heating treatment is performed in an atmospheric pressure atmosphere using a roll.
6) The pressure heat treatment is performed separately in a pressure process and a heating process, and after pressurizing at a temperature of less than 120 ° C., heating at a low pressure or normal pressure at a temperature of 120 ° C. or more is performed 1) to The manufacturing method of the laminated body in any one of 5).

7) A laminate of a support and a polyimide film, wherein a coupling agent layer is interposed between the support and the polyimide film, and the coupling agent layer is a predetermined layer composed of regions having different amounts of the coupling agent. A laminate having the following pattern.
8) The laminate according to 7) above, wherein the thickness unevenness of the polyimide film is 20% or less.

9) A method for producing a structure in which a device is formed on a polyimide film, wherein the laminate described in 7) or 8) above having a support, a polyimide film, and a coupling agent layer is used. After forming a device on the polyimide film of the laminate,
A method of manufacturing a device structure, comprising cutting a polyimide film in a region where the amount of the coupling agent is small and peeling the polyimide film from the support.
10) The method for producing a device structure according to 9), including a step of exposing the laminated body to a high temperature of 250 ° C. or higher when forming the device.

  According to the present invention, when laminating a support and a polyimide film via a coupling agent layer, a predetermined pattern consisting of regions with different amounts of coupling agent is formed, so when forming a device on the polyimide film In this process, the polyimide film can be easily separated from the support after the device is formed. Moreover, since the laminate of the present invention is obtained by bonding polyimide films having high heat resistance without using an adhesive or a pressure-sensitive adhesive, the laminate exhibits high heat resistance, and the laminate has a high temperature (for example, when a device is formed) The present invention can be favorably applied to a device forming process including a step exposed to 200 ° C. or higher, particularly 250 ° C. or higher. Such a laminate of the present invention is useful for producing a device structure in which devices such as a semiconductor element, a MEMS element, and a display element are formed on a film substrate.

FIG. 1 is a schematic view showing an embodiment of a method for producing a laminate according to the present invention. FIG. 2 is a schematic view showing one embodiment of the method for producing a device structure of the present invention. FIG. 3 is a schematic diagram showing a pattern example. FIG. 4 is an AFM image showing the crater portion. FIG. 5 is a cross-sectional AFM image of the straight portion of the crater portion shown in FIG. FIG. 6 is an AFM image (10 μm square) including a crater portion. FIG. 7 is an explanatory diagram for explaining a method of measuring the diameter of the crater portion. FIG. 8 is an explanatory diagram for explaining a method of measuring the number of craters.

(Laminate manufacturing method)
The manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body of a support body and a polyimide film.

<Support>
The support in the present invention may be a plate made of an inorganic material that can be used as a substrate, for example, a glass plate, a ceramic plate, a silicon wafer, a metal wafer or the like mainly, and these glass plates, Examples of the ceramic plate, silicon wafer, and metal composite include those obtained by laminating them, those in which they are dispersed, and those containing these fibers.

  Examples of the glass plate include 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), aluminosilicate glass and the like are included. Among these, those having a linear expansion coefficient of 5 ppm / ° C. or less are desirable, and if it is a commercial product, “Corning (registered trademark) 7059” or “Corning (registered trademark) 1737” manufactured by Corning, which is a glass for liquid crystal, “EAGLE”, “AN100” manufactured by Asahi Glass, “OA10” manufactured by Nippon Electric Glass, “AF32” manufactured by SCHOTT, etc. are desirable.

Examples of the ceramic plate include Al ₂ O ₃ , Mullite, AlN, SiC, Si ₃ N ₄ , BN, crystallized glass, Cordierite, Spodumene, Pb-BSG +.
CaZrO ₃ + Al ₂ O ₃ , Crystallized glass + Al ₂ O ₃ , Cr
ystallized Ca-BSG, BSG + Quartz, BSG + Quartz, BSG + Al ₂ O ₃ , Pb + BSG + Al ₂ O ₃ , Glass-ceramic, Zero-durer ceramics for substrates, TiO ₂ , Strontium titanate, Calcium titanate, Magnesium titanate, MgO, MgO _{steatite, BaTi 4 O 9, BaTiO 3} , BaTi 4 + CaZrO 3, BaSrCaZrTiO 3, Ba (TiZr) O 3, capacitor materials such as PMN-PT or _{PFN-PFW, PbNb 2 O 6} , Pb 0.5 Be 0.5 Nb 2 O ₆ , piezoelectric materials such as PbTiO ₃ , BaTiO ₃ , PZT, 0.855PZT-95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, and PLZT are included.

The silicon wafer includes all of n-type or p-type doped silicon wafers, intrinsic silicon wafers, etc., and silicon wafers in which a silicon oxide layer or various thin films are deposited on the surface of the silicon wafer. In addition to silicon wafers, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, and nitrogen-phosphorus-arsenic-antimony are often used. Furthermore, general-purpose semiconductor wafers such as InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), and ZnSe (zinc selenide) are also included.

  Examples of the metal include single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as inconel, monel, mnemonic, carbon copper, Fe-Ni invar alloy, and super invar alloy. In addition, a multilayer metal plate formed by adding other metal layers and ceramic layers to these metals is also included. 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 adhesion to the polyimide film, no diffusion, and good chemical resistance and heat resistance. Although it is not, chromium, nickel, TiN, and Mo containing Cu are mentioned as a suitable example.

  It is desirable that the planar portion of the support is sufficiently flat. Specifically, the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If it is rougher than this, the peel strength between the polyimide film and the support may be insufficient.

<Polyimide film>
In general, a polyimide film is obtained by reacting a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent with a support for preparing a polyimide film (the support here is a laminate of the present invention). And a green film (also referred to as a “precursor film” or a “polyamic acid film”) by coating and drying on a support for making a polyimide film, Alternatively, it can be obtained by subjecting the green film to a high-temperature heat treatment in a state where it is peeled off from the support to cause a dehydration ring closure reaction.

  The diamines constituting the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like that are usually used for polyimide synthesis can be used. Aromatic diamines having a benzoxazole structure are more preferable. Diamines may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as diamine which comprises a polyamic acid, The aromatic diamine, aliphatic diamine, alicyclic diamine etc. which are normally used for a polyimide synthesis | combination can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, it is possible to develop a high elastic modulus, a low heat shrinkage, and a low linear expansion coefficient as well as a high heat resistance. Diamines may be used alone or in combination of two or more.

  The aromatic diamine having a benzoxazole structure is not particularly limited. For example, 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5 -Amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 2,2'-p-phenylenebis (5-aminobenzoxazole), 2,2 ' -P-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6-aminobenzoxazolo) benzene, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (4,4′-diaminodiphenyl) benzo [1,2-d 4,5-d '] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2,6- (3,4 ' -Diaminodiphenyl) benzo [1,2-d: 4,5-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] Examples thereof include bisoxazole and 2,6- (3,3′-diaminodiphenyl) benzo [1,2-d: 4,5-d ′] bisoxazole.

Examples of the aromatic diamine other than the aromatic diamine having the benzoxazole structure described above include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl). ) -2-propyl] benzene (bisaniline), 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propyl Pan, 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′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,3′- Diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzo Zophenone, 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-aminophenoxy) 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-amino) Phenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminopheno) Cis) phenyl] butane, 1,4-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-aminophenoxy) -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-he Xafluoropropane, 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-aminophenoxy) 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) benzo 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} phenyl] sulfone, 1,4-bis [4 -(4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(4-Amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fur) Olophenoxy) -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′-diphenoxybenzophenone 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′-dia No-5,5′-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-bi Phenoxybenzophenone, 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-biphenoxybenzoy) ) Benzene, 1,3-bis (4-amino-5-biphenoxy benzoyl) benzene, 1
, 4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, and the aromatic ring of the above aromatic diamine Some or all of the above hydrogen atoms are substituted by halogen atoms, some or all of the hydrogen atoms of a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, a cyano group, or an alkyl group or alkoxyl group. An aromatic diamine substituted with a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxyl group is exemplified.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and the like.
Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (2,6-dimethylcyclohexylamine), and the like.
The total amount of diamines other than aromatic diamines (aliphatic diamines and alicyclic diamines) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of the total diamines. It is. In other words, the aromatic diamine is preferably 80% by mass or more of the total diamines, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

  The tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including acid anhydrides), aliphatic tetracarboxylic acids (including acid anhydrides), and alicyclic tetracarboxylic acids that are commonly used for polyimide synthesis. Acids (including acid anhydrides thereof) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and alicyclic from the viewpoint of light transmission. Group tetracarboxylic acids are more preferred. In the case where these are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydrides) are preferred. Good. Tetracarboxylic acids may be used alone or in combination of two or more.

Examples of the alicyclic tetracarboxylic acids include alicyclic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3 ′, 4,4′-bicyclohexyltetracarboxylic acid. Carboxylic acids and their acid anhydrides are mentioned. Among these, dianhydrides having two anhydride structures (for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Bicyclohexyltetracarboxylic dianhydride and the like) are preferred. In addition, alicyclic tetracarboxylic acids may be used independently and may use 2 or more types together.
In the case where importance is attached to transparency, the alicyclic tetracarboxylic acids are, for example, preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and further preferably 95% by mass or more.

The aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably acid anhydrides thereof. Examples of such aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 , 3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis [4- (3,4-di Carboxyphenoxy) phenyl] propanoic anhydride and the like.
In the case of placing importance on heat resistance, the aromatic tetracarboxylic acids are, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of all tetracarboxylic acids.

  The solvent used in the reaction (polymerization) of diamines and tetracarboxylic acids to obtain a polyamic acid is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. Solvents are preferred, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric Examples include amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents may be used alone or in combination of two or more. The amount of these solvents used may be an amount sufficient to dissolve the raw material monomer. As a specific amount used, the amount of all monomers in the reaction solution (solution in which the monomer is dissolved) is usually The amount is 5 to 40% by mass, preferably 10 to 30% by mass.

  The conditions for the polymerization reaction (hereinafter also simply referred to as “polymerization reaction”) for obtaining the polyamic acid may be conventionally known conditions, for example, in an organic solvent at a temperature range of 0 to 80 ° C. for 10 minutes. Stirring and / or mixing continuously for ˜30 hours. If necessary, the polymerization reaction may be divided or the reaction temperature may be increased or decreased. Although there is no restriction | limiting in particular in the addition order of a monomer, It is preferable to add tetracarboxylic acids in the solution of diamines.

  Further, vacuum degassing during the polymerization reaction is also effective for producing a good quality polyamic acid solution. Further, the polymerization may be controlled by adding a small amount of a terminal blocking agent to the diamine before the polymerization reaction. Examples of the terminal blocking agent include dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and aniline derivatives. Among these, specifically, phthalic anhydride, maleic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, and ethynylaniline are preferable, and maleic anhydride is particularly preferable. The amount of the end-capping agent used is preferably 0.001 to 1.0 mol with respect to 1 mol of the diamine.

  The mass of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The viscosity of the polyamic acid solution is preferably 10 to 2000 Pa · s, more preferably 100 to 1000 Pa · s, as measured by a Brookfield viscometer (25 ° C.), from the viewpoint of liquid feeding stability. .

  Various additives such as an antifoaming agent, a leveling agent, and a flame retardant may be added to the polyamic acid solution obtained by the polymerization reaction for the purpose of further improving the performance of the polyimide film. These addition methods and addition times are not particularly limited.

In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (self-supporting precursor film) is obtained by applying and drying the polyamic acid solution on a polyimide film production support, Next, a method of imidizing the green film by subjecting it to a heat treatment can be employed. Application of polyamic acid solution to the support includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, casting from a nozzle with a slit, extruder However, the present invention is not limited thereto, and conventionally known solution coating means can be appropriately used. What is necessary is just to set the application quantity of a polyamic-acid solution suitably according to the film thickness of the desired polyimide film. The heating temperature for drying the applied polyamic acid solution is preferably 50 ° C to 120 ° C, more preferably 80 ° C to 100 ° C. The drying time is preferably 5 minutes to 3 hours, more preferably 15 minutes to 2 hours. The residual solvent amount in the green film after drying is preferably 25 to 50% by mass, and more preferably 35 to 45% by mass. The temperature at the time of heat-treating the green film is preferably, for example, 150 to 550 ° C, more preferably 280 to 520 ° C. The heat treatment time is desirably 0.05 to 10 hours.

  The polyimide film has a glass transition temperature of 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or preferably no glass transition point is observed in the region of 500 ° C. or lower. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC).

  The average coefficient of linear expansion (CTE) between 30 ° C. and 300 ° C. of the polyimide film is preferably −5 ppm / ° C. to +20 ppm / ° C., more preferably −5 ppm / ° C. to +15 ppm / ° C. Preferably, it is 1 ppm / ° C. to +10 ppm / ° C. When the CTE is in the above range, the difference in coefficient of linear expansion from a general support can be kept small, and the polyimide film and the support made of an inorganic material can be prevented from being peeled even when subjected to a process of applying heat. .

  Although the thickness of the polyimide film in this invention is not specifically limited, 1 micrometer-200 micrometers are preferable, More preferably, they are 3 micrometers-120 micrometers, More preferably, they are 3 micrometers-60 micrometers. It can be easily applied to narrow parts and can greatly contribute to the enhancement of the performance of elements such as sensors and the miniaturization of electronic parts. If the thickness of the polyimide film is less than 1 μm, it is difficult to strictly control the thickness, and peeling from the support becomes difficult. On the other hand, if it exceeds 200 μm, the polyimide film is bent when it is peeled off from the support. Is likely to occur.

The thickness unevenness of the polyimide film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow portions. In addition, the thickness unevenness of a film can be calculated | required based on the following formula, for example, extracting about 10 points | pieces positions from a film to be measured at random with a contact-type film thickness meter, measuring film thickness.
Film thickness spots (%)
= 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

  The polyimide film is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of production, and a form of a roll-shaped polyimide film wound on a winding core Are more preferred.

In the polyimide film, in order to ensure handling and productivity, a sliding material (particle) is added to and contained in the polyimide constituting the film, and the surface of the polyimide film is given fine irregularities to ensure slipperiness. It is preferable.
The lubricant (particle) is a fine particle made of an inorganic substance, and includes metal, metal oxide, metal nitride, metal carbonized product, metal acid salt, phosphate, carbonate, talc, mica, clay, and other clay minerals. , Etc. can be used. Preferably, metal oxides such as silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, phosphates, and carbonates can be used. Only one type of lubricant may be used, or two or more types may be used.

  The volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 μm, preferably 0.03 to 2.5 μm, more preferably 0.05 to 0.7 μm, still more preferably 0.05 to 0.3 μm. The volume average particle diameter is based on a measurement value obtained by a light scattering method. If the particle diameter is smaller than the lower limit, industrial production of the polyimide film becomes difficult. If the particle diameter exceeds the upper limit, the unevenness of the surface becomes too large and the pasting strength becomes weak, which may cause practical problems.

  The addition amount of the lubricant is 0.05 to 50% by mass, preferably 0.1 to 3% by mass, more preferably 0.2 to 1% by mass with respect to the polymer solid content in the polyamic acid solution. %. If the amount of the lubricant added is too small, it is difficult to expect the effect of the lubricant addition, and there is a case that the slipperiness is not secured so much that the polyimide film production may be hindered. Even if the slipperiness is ensured, there is a possibility that the smoothness is lowered, the breaking strength and breaking elongation of the polyimide film are lowered, and the CTE is raised.

  When a lubricant (particle) is added to and contained in a polyimide film, it may be a single-layer polyimide film in which the lubricant is uniformly dispersed. For example, one surface is composed of a polyimide film containing a lubricant, Even if the other surface does not contain or contains a lubricant, a multilayer polyimide film composed of a polyimide film having a small amount of lubricant may be used. In such a multilayer polyimide film, fine irregularities are imparted to the surface of one layer (film), and slipperiness can be secured with the layer (film), and good handling properties and productivity can be secured. . Hereinafter, the production of such a multilayer polyimide film will be described.

The multilayer polyimide film is, for example, a polyamic acid solution (polyimide precursor solution) with a lubricant (preferably having an average particle size of about 0.05 to 2.5 μm) of 0 per polymer solids in the polyamic acid solution. 0.05% to 50% by mass (preferably 0.1 to 3% by mass, more preferably 0.20 to 1% by mass) and no lubricant or a small amount (preferably It is preferable to produce using two polyamic acid solutions that are 0.3% by mass or less, more preferably 0.01% by mass or less) based on the solid content of the polymer in the polyamic acid solution.
The method of multilayering (lamination) of the multilayer polyimide film is not particularly limited as long as no problem occurs in the adhesion between the two layers, and any method may be used as long as the adhesion is achieved without using an adhesive layer or the like. For example, i) a method in which one polyimide film is prepared and then the other polyamic acid solution is continuously applied onto the polyimide film to imidize; ii) one polyamic acid solution is cast to produce a polyamic acid film. After this, the other polyamic acid solution is continuously applied onto the polyamic acid film and then imidized, iii) a method by coextrusion, iv) a polyamic acid which does not contain a lubricant or has a small content Examples thereof include a method in which a polyamic acid solution containing a large amount of a lubricant is applied on a film formed by a solution by spray coating, T-die coating, or the like, and imidized. The methods i) and ii) are preferable.

  The ratio of the thickness of each layer in the multilayer polyimide film is not particularly limited, but the film (layer) formed of the polyamic acid solution containing a large amount of the lubricant (a) layer, does not contain the lubricant or contains it Assuming that the film (layer) formed of the polyamic acid solution in a small amount is the (b) layer, the (a) layer / (b) layer is preferably 0.05 to 0.95. If the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost. On the other hand, if it is less than 0.05, the effect of improving the surface properties is insufficient and the slipperiness is lost. May be.

  The polyimide film is preferably subjected to plasma treatment in advance on at least the surface facing the support. By applying the plasma treatment, the surface of the polyimide film is modified to have a functional group (so-called activated state), and adhesion to the support is improved.

The plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Also includes ion implantation using a source, processing using a PBII method, frame processing, intro processing, and the like. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.

Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF ₄ and C ₂ F _6, plasma known to have a high etching effect, or physical energy such as Ar plasma. It is desirable to use plasma with a high effect of applying to the polyimide surface and physically etching. Further, it is also preferable to add plasma such as CO ₂ , H ₂ , N ₂ , a mixed gas thereof, and further water vapor. When aiming at processing in a short time, a plasma having a high plasma energy density, a high kinetic energy of ions in the plasma, and a high number density of active species are desirable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, PBII method, and the like are also desirable.

  The effects of plasma treatment include the addition of the above-mentioned surface functional groups, the change in contact angle accompanying this, improvement in adhesion, removal of surface contamination, etc., as well as the removal of irregularly shaped objects associated with processing called desmear. There is a surface etching effect such as removal. In particular, since polymer and ceramic are completely different in etching ease, only a polymer having a lower binding energy than ceramic is selectively etched. For this reason, under the gas species and discharge conditions that have an etching action, only the polymer is selectively etched to expose the lubricant (also referred to as particles or filler). In addition to the above plasma treatment, as a means of obtaining an etching effect on the film surface, polishing with a pad including the case where a chemical solution is used in combination, brush polishing, polishing with a sponge soaked with a chemical solution, and putting abrasive particles in the polishing pad Examples include polishing with sand, sand blasting, wet blasting, and the like, and these means may be employed together with plasma treatment.

  The plasma treatment may be performed only on one side of the polyimide film or on both sides. When performing plasma treatment on one side, it is possible to perform plasma treatment only on the side of the polyimide film that is not in contact with the electrode by placing the polyimide film in contact with the electrode on one side in the plasma treatment with parallel plate electrodes. it can. If a polyimide film is placed in a state where it is electrically floated in the space between the two electrodes, plasma treatment can be performed on both sides. Moreover, single-sided processing becomes possible by performing plasma processing in the state which stuck the protective film on the single side | surface of the polyimide film. In addition, as a protective film, a PET film with an adhesive or an olefin film can be used.

The polyimide film subjected to the plasma treatment is preferably subjected to an acid treatment after the plasma treatment. On the polyimide film surface containing the lubricant (particles), even if the lubricant has a convex shape near the surface, a very thin polyimide layer exists on the surface. Since polyimide has strong resistance to acid, even if it is a very thin layer, if polyimide is on the surface of the lubricant, the acid will not be in direct contact with the surface of the lubricant and will not be eroded by the acid treatment. After only the polymer (polyimide) is selectively etched due to the effect, the acid directly contacts the surface of the lubricant. Therefore, if an appropriate acid type is selected and acid treatment is performed, only the lubricant can be obtained in a very short time. Dissolution removal can be performed and a crater is formed.
This crater is considered to be the remaining part in which the lubricant exposed from the polyimide film surface by the plasma treatment is eluted by the acid, and is not a mere dent but a dent with its edge raised. As a reference, FIG. 4 shows an AFM image showing the crater part, FIG. 5 shows a cross-sectional image of the straight part of the crater part shown in FIG. 4, and FIG. 6 shows an AFM image (10 μm square) including the crater part. The edge portion of the crater is softer than the protrusion in which the lubricant particles are encapsulated, and is deformed with a relatively weak force when the polyimide film and the support are brought into pressure contact. The protrusion containing the lubricant is not easily deformed and inhibits the adhesion between the polyimide film and the support, but the adhesion between the polyimide film and the support is achieved by making the lubricant part into such a crater-like shape. And the peel strength between the polyimide film and the support can be further improved.

  The acid treatment can be performed by immersing the plasma-treated polyimide film in a chemical solution containing acid, or by applying or spraying the chemical solution on the plasma-treated polyimide film. You may use washing together. Moreover, the acid treatment of only one side becomes possible by performing an acid treatment in the state which stuck the protective film on the single side | surface of the polyimide film. As the protective film, a PET film with an adhesive or an olefin film can be used.

As the acid used for the acid treatment, those capable of etching only the lubricant are preferable. For example, HF and BHF having an action of dissolving SiO ₂ and glass are preferably used, and these are usually used as an aqueous solution. For example, since SiO ₂ (etching dissolution efficiency) of a 10% by mass HF aqueous solution is about 12 cm / sec at room temperature, an SiO ₂ lubricant of about 80 nm can be sufficiently processed by contact with a chemical solution for about 1 minute. Become. Therefore, when acid treatment with an HF aqueous solution or a BHF aqueous solution is performed, it is preferable to use SiO ₂ as a lubricant, but of course, the type of the lubricant is not limited to SiO ₂ .
As for the acid concentration in a chemical | medical solution, 20 mass% or less is preferable, More preferably, it is 3-10 mass%. If the acid concentration in the chemical solution is too thin, the etching time takes a long time and the productivity is lowered. If the acid concentration is too high, the etching time is too fast and the chemical solution is exposed more than necessary.

  The step of applying plasma treatment and acid treatment to the polyimide film (raw fabric) is preferably performed by roll-to-roll from the viewpoint of increasing the efficiency of the treatment. Since the polyimide film roll subjected to the plasma treatment also has a lubricant, the handling property as a roll is equivalent to that before the plasma treatment. Moreover, after performing plasma treatment with a roll, it is also useful to perform acid treatment after making it into a cut sheet from the viewpoint that simple implementation is possible.

As described above, the surface morphology of the polyimide film subjected to the plasma treatment and the acid treatment has ² to 100 craters having a diameter of 10 to 500 nm per 100 μm ² when one surface thereof is observed by the AFM method described later. Preferably, Ra on the other surface is 0.3 nm to 0
. The thickness is preferably 95 nm, whereby the adhesiveness is improved, and a surface having a smoothness suitable for bonding and lamination without an adhesive with the support is provided.

A polyimide film having ² to 100 craters having a diameter of 10 to 500 nm on one side per 100 μm ² has a more appropriate peel strength in bonding lamination without an adhesive with a support. Preferably, the number of craters is 5-30 per 100 μm ² and the crater diameter is 30-100 nm. If the diameter of the crater is less than 10 nm, the effect of improving the adhesiveness will be reduced, and if it exceeds 500 nm, excessive etching will be performed, which will adversely affect the strength of the polyimide film and will also have an effect on improving the adhesiveness. It becomes difficult. When the number of craters is less than 2, the effect of improving the adhesiveness is reduced, and when the number of craters exceeds 100, the polyimide film strength is adversely affected and the effect of improving the adhesiveness is hardly exhibited.

It is particularly preferable that Ra on the other surface of the polyimide film is a smooth surface having a thickness of 0.3 nm to 0.95 nm in order to produce a precise electric circuit or semiconductor device. For example, when Ra exceeds 2.0 nm. In other words, it does not have the necessary degree of smoothness, and may adversely affect the metal foil film formed thereon in terms of adhesion and smoothness. Such a polyimide film having a smooth surface is produced by using a polyamide acid solution for forming a polyimide (polyimide precursor solution) with a combination of a lubricant and a non-added or a very small amount. In addition, roll roll-up property and proper slipping property at the time of polyimide film production are also given, and the polyimide film production becomes easy.

<Coupling agent layer>
In the laminate of the present invention, a coupling agent layer formed by applying a coupling agent is interposed between the support and the polyimide film, and the coupling agent layer has a coupling agent amount. It has a predetermined pattern consisting of different areas. Here, having a predetermined pattern means that a region having a large amount and a region having a small amount of the coupling agent (attachment amount; specifically, the total amount of the coupling agent in each region) exist in a predetermined pattern. This means that the region where the agent is present and the region where the coupling agent is not present exist in a predetermined pattern, and the former is a method of printing a predetermined pattern by changing the halftone dot. The embodiment includes a mode in which a coupling agent is applied with a difference in a fine coating area depending on a size or a thin line, and a region having a large area and a region having a small area are present in a predetermined pattern. In this way, if patterning is performed depending on the amount or amount of coupling agent (covering area), it is sufficient to prevent peeling at the time of device formation in a region where a large amount of coupling agent intervenes (hereinafter also referred to as “good adhesion portion”). Polyimide film on which a device is mounted by cutting and peeling the polyimide film in a region where only a small amount of coupling agent is present or not present at all (hereinafter also referred to as “easy peeling part”) Can be easily separated from the support.

  In order to form a predetermined pattern depending on the presence or absence of the amount of coupling agent, the coupling agent may be directly applied or diluted with a solvent or the like and partially applied to the support. For example, inkjet printing or gravure printing , Selectively applied only to a region to be a good adhesion portion by one or more coating methods selected from the group consisting of screen printing, planographic printing, reverse printing, microcontact printing, and dispenser coating, or an easily peelable portion The region may be covered with a mask or the like in advance, and after the entire surface is coated from above, the mask may be removed. As another partial application method, for example, a method of attaching a coupling agent only to a region to be a good adhesion portion using a stamp such as a mouth shape or a square shape, or a region to be an easily peelable portion is surrounded. It is also possible to use a method in which a coupling agent is attached to the support using a stamp having a shape (for example, a square shape), and then the coating agent is spread around the area to be easily peeled by spin coating. it can.

  In order to form a predetermined pattern depending on the amount of the coupling agent, the coupling agent may be directly or diluted with a solvent or the like, and the coating amount may be partially changed according to the pattern. The coating amount is preferably a method of changing the microscopic covering area by the coupling agent depending on the size of fine dots such as printing halftone dots. In order to change the coating area and separately coat, for example, one or more coating methods selected from the group consisting of inkjet printing, gravure printing, screen printing, planographic printing, reversal printing, microcontact printing, and dispenser coating may be employed. it can. According to such printing technology and direct drawing technology, regions (good adhesion portion and easy peeling portion) having different coupling agent amounts can be formed by changing the setting of dot density (area density). At this time, the area density due to the halftone dots of the well-bonded portion is 1.5 times or more, preferably twice or more, more preferably 2.5 times or more than the area density due to the halftone dots of the easily peelable portion.

  As another method of changing the coating amount by changing the amount of coupling agent applied, for example, a shape that surrounds the region to be easily peeled and has a line inside the region (for example, a Japanese character shape or a rice field shape) It is also possible to employ a method in which the coupling agent is attached to the support using the stamp of), and then the support is spin-coated under an appropriate rotational condition. At this time, if the rotation speed of the support is too high or if the rotation time is too long, there may be no difference in the coating amount between the area where the coupling agent is directly attached and the other area, It is desirable to rotate under conditions (for example, about 10 to 30 seconds at a rotation speed of 500 to 1800 rpm).

  Further, as another method of coating by changing the coating amount of the coupling agent, for example, the coupling agent is printed on the entire surface of the support, dried as necessary, and further overlapped on the region to be a good adhesion portion. It is also possible to adopt a method in which the amount of coating is partially increased in several steps, such as printing a coupling agent.

  After applying the coupling agent, heat treatment is usually applied. The conditions during the heat treatment are preferably 50 to 250 ° C., more preferably 75 to 165 ° C., more preferably about 95 to 155 ° C., preferably 30 seconds or more, more preferably 2 minutes or more, still more preferably What is necessary is just to heat for 5 minutes or more. If the heating temperature is too high, decomposition or inactivation of the coupling agent may occur, and if it is too low, fixing will be insufficient. Moreover, even if the heating time is too long, the same problem may occur. The upper limit of the heating time is preferably 5 hours, more preferably about 2 hours.

  The film thickness of the coupling agent layer (thickness in the good adhesion part and easy peeling part) is extremely thin compared to the support, polyimide film or general adhesives and pressure-sensitive adhesives. The thickness is negligible from the viewpoint. In principle, a thickness of the order of a monomolecular layer is sufficient as a minimum. Generally, it is less than 400 nm (less than 0.4 μm), preferably 200 nm or less (0.2 μm or less), more practically 100 nm or less (0.1 μm or less), more preferably 50 nm or less, further preferably 10 nm or less. It is. For processes that desire as little coupling agent as possible, 5 nm or less is possible. However, if the thickness is less than 1 nm, the peel strength may be reduced, or a portion that is not partially attached may appear, and therefore, 1 nm or more is preferable. The film thickness of the coupling agent layer can be determined by ellipsometry or calculation from the concentration of the coupling agent solution at the time of coating and the coating amount.

  The pattern shape may be appropriately set according to the type of device to be stacked, and is not particularly limited. An example is as shown in FIG. 3. As shown in FIG. 3 (1), the good adhesion portion 10 is arranged only at the outer peripheral portion of the laminate, and the easy peeling portion 20 is arranged inside the laminate. Pattern (such as a square shape) or a pattern in which the good adhesion portion 10 is arranged linearly inside the outer periphery of the laminate as shown in FIG. ).

The coupling agent may be a compound that physically or chemically intervenes between the support and the polyimide film and has an effect of increasing the adhesive force between the two. For example, a silane coupling agent or a phosphorus-based compound Examples include coupling agents and titanate coupling agents. Among these, a silane coupling agent is particularly preferable, and a silane coupling agent having an amino group or an epoxy group is particularly preferable.
Preferable specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltriethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyl Limethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate Chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and the like.

As the coupling agent that can be used in the present invention, in addition to the above, for example, 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, butyl 3-mercaptopropionate, 3- (dimethoxymethylsilyl) -1-propanethiol, 4- (6-mercaptohexaloyl) benzyl alcohol, 11-amino-1-undecenethiol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoro Acetic acid, 2,2 ′-(ethylenedioxy) diethanethiol, 11-mercaptoundecyltri (ethylene glycol), (1-mercaptoundec-11-yl) tetra (ethylene glycol), 1- (methylcarboxy) Undec-11-yl) hexa (eth) Lenglycol), hydroxyundecyl disulfide, carboxyundecyl disulfide, hydroxyhexadodecyl disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, titanium dioctyloxybis (octylene glycolate), zirconium tributoxy monoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltri Chlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethyl Silane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane, n -Octyltriethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, pentyltriethoxysilane, pentyltrichlorosilane, triacetoxymethylsilane, trichlorohexylsilane , Trichloromethylsilane, trichlorooctadecylsilane, trichloropropylsilane, trichlorotetra Silsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trichloro-2- Cyanoethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2,3-butanedithiol, 1-butanethiol, 2-butanethiol, cyclohexane Thiol, cyclopentanethiol, 1-decanethiol, 1-dodecanethiol, 3-mercaptopropionic acid-2-ethylhexyl , Ethyl 3-mercaptopropionate, 1-heptanethiol, 1-hexadecanethiol, hexyl mercaptan, isoamyl mercaptan, isobutyl mercaptan, 3-mercaptopropionic acid, 3-methoxybutyl 3-mercaptopropionic acid, 2-methyl-1 -Butanethiol, 1-octadecanethiol, 1-octanethiol, 1-pentadecanethiol, 1-pentanethiol, 1-propanethiol, 1-tetradecanethiol, 1-undecanethiol, 1- (12-mercaptododecyl) imidazole, 1 -(11-mercaptoundecyl) imidazole, 1-
(10-mercaptodecyl) imidazole, 1- (16-mercaptohexadecyl) imidazole, 1- (17-mercaptoheptadecyl) imidazole, 1- (15-mercapto) dodecanoic acid, 1- (11-mercapto) undecanoic acid, 1- (10-mercapto) decanoic acid and the like can also be used.

  Particularly preferred coupling agents 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-dimethyl-butylidene) propylamine, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, amino Phenethyltrimethoxysilane, aminopheny Such as aminomethyl phenethyltrimethoxysilane the like. In the case where particularly high heat resistance is required in the process, it is desirable to use an aromatic group between Si and an amino group.

<Pressurized heat treatment>
The laminate of the present invention is produced by superposing the support provided with a coupling agent layer on the polyimide film and subjecting the laminate to pressure and heat treatment.

  The pressure heat treatment may be performed while heating a press, a laminate, a roll laminate, or the like, for example, in an atmospheric pressure atmosphere or in a vacuum. A method of heating under pressure in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, press or roll lamination in an air atmosphere is preferable, and a method using rolls (roll lamination or the like) is particularly preferable.

The pressure during the pressure heat treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be damaged. If the pressure is too low, a non-adhering portion may be produced, resulting in insufficient adhesion. The temperature during the pressure heat treatment is 150 ° C to 400 ° C, more preferably 250 ° C to 350 ° C. If the temperature is too high, the polyimide film may be damaged. If the temperature is too low, the adhesion tends to be weak.
The pressure heat treatment can be performed in an atmospheric pressure atmosphere as described above. However, in order to obtain a stable peel strength on the entire surface, it is preferably performed under vacuum. At this time, the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
As an apparatus that can be used for pressure heat treatment, for example, “11FD” manufactured by Imoto Seisakusho can be used to perform pressing in a vacuum, and a roll-type film laminator in vacuum or a vacuum is used. For example, “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used to perform vacuum laminating such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.

  The pressure heat treatment can be performed separately in a pressure process and a heating process. In this case, first, the polyimide film and the support are pressurized (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, a temperature of less than 120 ° C., more preferably 95 ° C. or less) to ensure adhesion between the two. Thereafter, at a low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or a relatively high temperature at normal pressure (for example, 120 ° C. or more, more preferably 120 to 250 ° C., further preferably 150 to 230 ° C.). By heating with, the chemical reaction at the adhesion interface is promoted and the polyimide film and the support can be laminated.

  In general, as a method of obtaining a laminate of a support and a polyimide film, a method in which a polyimide varnish (polyamic acid solution described above) is directly applied on the support and imidized to form a film is also considered. In the invention, the polyimide is formed into a film and then laminated on the support. For example, when a polyamic acid solution is imidized by heating on a support, for example, although it depends on the support, a concentric film thickness distribution can be easily formed, and the state of the front and back of the polyimide film (transfer of heat) This is because the film tends to be warped or lifted from the support due to the difference in the method, etc., whereas these problems can be avoided if the film is formed in advance. Furthermore, by superimposing the film on the support, it is possible to form a device (circuit or the like) on the film before superposition within a range where pressure heating treatment described later can be performed.

<Application>
In the method for producing a laminate of the present invention, as an application example, a polyimide film in the laminate or a hole portion penetrating in the film thickness direction of the entire laminate is provided as necessary, thereby providing a non-polyimide portion. Also good. 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. And a hole in which a metal film is formed on the wall surface of the hole by sputtering, electroless plating seed layer formation, or the like.

(Laminate)
In the laminate of the present invention, a coupling agent layer is interposed between the support and the polyimide film, and the coupling agent layer has a predetermined pattern in which the amount of the coupling agent is different. Thereby, after producing a device on a polyimide film without peeling even in a high temperature process at the time of device production, it becomes a laminated body which can peel a polyimide film from a support easily. The laminate of the present invention can be obtained by the method for producing a laminate of the present invention, and details of the support, polyimide film, coupling agent layer and the like are as described above.

  In the present invention, the 180-degree peel strength between the support and the polyimide film may be appropriately set according to the type and process of the device laminated thereon, and is not particularly limited. The 180-degree peel strength is preferably 1/2 or less, more preferably 1/5 or less of the 180-degree peel strength of the good adhesion portion. As a general theory, the 180 degree peel strength of the good adhesion portion is preferably 0.5 N / cm or more and 5 N / cm or less, more preferably 0.8 N / cm or more and 2 N / cm or less. The 180 degree peel strength of the easy peel portion is preferably 0.01 N / cm or more and 0.4 N / cm or less, more preferably 0.01 N / cm or more and 0.2 N / cm or less. Here, the lower limit of the 180-degree peel strength of the easily peelable portion is a value that takes into account the bending energy of the polyimide film. 180 degree peel strength in this invention can be measured by the method mentioned later in an Example. In addition, the heat-resistant peel strength, acid peel strength, and alkali peel strength, which will be described later in the examples, are preferably 0.5 N / cm or more and 5 N / cm or less, respectively. There can be.

(Device structure manufacturing method)
The method for producing a device structure of the present invention is a method for producing a structure in which a device is formed on a polyimide film as a substrate, using the laminate of the present invention having a support and a polyimide film. .
In the manufacturing method of the device structure of the present invention, after forming a device on the polyimide film of the laminate of the present invention, the polyimide film in the easily peelable part of the laminate is cut and the polyimide film is used as the support. Peel from.

  As a method of cutting into the polyimide film of the easily peelable portion of the laminate, a method of cutting the polyimide film with a cutting tool such as a blade, or a method of cutting the polyimide film by relatively scanning the laser and the laminate There are a method of cutting the polyimide film by relatively scanning the water jet and the laminate, a method of cutting the polyimide film while cutting slightly to the glass layer with a semiconductor chip dicing device, etc., but the method is particularly limited. It is not a thing. For example, in adopting the above-described method, it is possible to appropriately employ a technique such as superimposing ultrasonic waves on the cutting tool or adding a reciprocating operation or an up-and-down operation to improve the cutting performance.

  When making a cut in the polyimide film of the easy-peeling portion of the laminate, it is sufficient that the position where the cut is made includes at least a part of the easy-peeling portion, and basically it is basically cut according to the pattern. However, if an attempt is made to accurately cut according to the pattern at the boundary between the good adhesion portion and the easy peeling portion, an error also occurs. Therefore, it is preferable to cut slightly to the easy peeling portion side from the pattern in terms of increasing productivity. Moreover, in order to prevent peeling without permission before peeling, there may be a production system that cuts into the bonded portion slightly better than the pattern. Furthermore, if the width of the good adhesion portion is set narrow, the polyimide film remaining in the good adhesion portion at the time of peeling can be reduced, the use efficiency of the film is improved, and the device area with respect to the laminate area is large. Thus, productivity is improved. Furthermore, an easy peeling part is provided in a part of the outer peripheral part of the laminated body, and the method in which the outer peripheral part is used as a cutting position and actually peeled off without making a cut is also an extreme form of the present invention. Yeah.

  The method of peeling the polyimide film from the support is not particularly limited, but is a method of rolling from the end with tweezers, etc., and sticking an adhesive tape to one side of the cut portion of the polyimide film with a device, and then rolling from the tape portion. A method, a method in which one side of a cut portion of a polyimide film with a device is vacuum-adsorbed and then wound from that portion can be employed. In the case of peeling, if a bend with a small curvature occurs in the cut part of the polyimide film with the device, stress may be applied to the device in that part and the device may be destroyed. It is desirable to remove. For example, 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 the roll having a large curvature is located at the peeling portion.

  In addition, the reinforcing member can be fixed before the device structure (polyimide film with a device) of the present invention is a final product. In this case, the reinforcing member may be fixed after being peeled off from the support, but after fixing the reinforcing member, the polyimide film is cut off and peeled off from the support, or the polyimide film is cut into It is preferable that the reinforcing member is fixed to the cut portion and then peeled off. In the case where the reinforcing member is fixed before peeling, it is possible to make the device part less susceptible to stress by considering the elastic modulus and film thickness of the polyimide film and the reinforcing member. For example, a PET film with an adhesive is attached as a reinforcing member only to the easily peelable portion of the laminate of the present invention, and a device with a device is formed by cutting the easy peelable portion with the adhesive PET film attached. The polyimide film may be peeled off, or a PET film with an adhesive is attached to the entire laminate of the present invention as a reinforcing member, and an easy-peeled portion of the laminate is cut to provide an PET film with an adhesive. You may make it peel a polyimide film with a device in the stuck state.

When the reinforcing member is fixed before peeling, a polymer film, ultrathin glass, SUS, or the like is preferably used as the reinforcing member. The polymer film has an advantage that the lightness of the device is maintained, and further includes transparency, various workability, and difficulty in cracking. Ultra-thin glass has the advantages of providing gas barrier properties, chemical stability, and transparency. SU
S has the advantage that it can be shielded electrically and is difficult to break. In addition, since it is after passing the process which already requires high temperature as a polymer film, there are few restrictions of heat resistance, and various polymer films can be selected. These reinforcing members can be fixed by adhesion or adhesion.

In the present invention, a method for forming a device on a polyimide film as a substrate may be appropriately performed according to a conventionally known method.
The device in the present invention is not particularly limited, and examples thereof include only electronic circuit wiring, electrical resistance, passive devices such as coils and capacitors, active devices including semiconductor elements, and electronic circuit systems that combine these devices. is there. Examples of the semiconductor element include a solar cell, a thin film transistor, a MEMS element, a sensor, and a logic circuit.

For example, in a film-like solar cell using the laminate of the present invention, a laminate X including a photoelectric conversion layer made of a semiconductor is formed on the base material of the polyimide film of the laminate of the present invention. . This laminated body X has a photoelectric conversion layer that converts sunlight energy into electric energy as an essential component, and usually further includes an electrode layer for taking out the obtained electric energy.
Hereinafter, a laminated structure in which a photoelectric conversion layer is sandwiched between a pair of electrode layers will be described as a typical example of the laminate X formed to constitute a film-like solar cell. However, a structure in which several photoelectric conversion layers are stacked can be said to be a solar cell of the present invention if it is produced by PVD or CVD. Of course, the laminated structure of the laminated body X is not limited to the embodiment described below, and the structure of the laminated body of the solar cell of the prior art may be appropriately referred to, and a protective layer and known auxiliary means may be added. It ’s good.

One electrode layer (hereinafter also referred to as a back electrode layer) of the pair of electrode layers is preferably formed on one main surface of the polyimide film substrate. The back electrode layer is obtained by laminating a conductive inorganic material by a conventionally known method, for example, a CVD (chemical vapor deposition) method or a sputtering method. Examples of the conductive inorganic material include metal thin films such as Al, Au, Ag, Cu, Ni, and stainless steel, In ₂ O ₃ , SnO ₂ , ZnO, and Cd ₂ SnO _4.
And oxide semiconductor-based conductive materials such as ITO (In ₂ O ₃ added with Sn). Preferably, the back electrode layer is a metal thin film. The thickness of the back electrode layer is not particularly limited, and is usually about 30 to 1000 nm. In addition, a film forming method that does not use a vacuum such as Ag paste may be adopted for a part of electrode extraction.

The photoelectric conversion layer for converting the energy of sunlight into electric energy is a layer made of a semiconductor, CuInSe ₂ which is a compound semiconductor thin film (chalcopyrite structure semiconductor thin film) made of a group I element, a group III element, and a group VI element. (CIS) film or Cu in which Ga is dissolved (
It is an In, Ga) Se ₂ (CIGS) film (hereinafter, both are collectively referred to as a CIS film) and a silicon semiconductor layer. Examples of the silicon-based semiconductor include a thin film silicon layer, an amorphous silicon layer, and a polycrystalline silicon layer. The photoelectric conversion layer may be a laminate having a plurality of layers made of different semiconductors. Moreover, the photoelectric converting layer using a pigment | dye may be sufficient. Further, an organic thin film semiconductor made of an organic compound such as a conductive polymer or fullerene may be used.

The thin film silicon layer is a silicon layer obtained by a plasma CVD method, a thermal CVD method, a sputtering method, a cluster ion beam method, a vapor deposition method, or the like.
The amorphous silicon layer is a layer made of silicon having substantially no crystallinity. The lack of crystallinity can be confirmed by not giving a diffraction peak even when irradiated with X-rays. Means for obtaining an amorphous silicon layer are known, and examples of such means include a plasma CVD method and a thermal CVD method.
The polycrystalline silicon layer is a layer made of an aggregate of microcrystals made of silicon. The above amorphous silicon layer is distinguished by giving a diffraction peak by irradiation with X-rays. Means for obtaining a polycrystalline silicon layer are known, and such means include means for heat-treating amorphous silicon.
The photoelectric conversion layer is not limited to a silicon-based semiconductor layer, and may be, for example, a thick film semiconductor layer. The thick film semiconductor layer is a semiconductor layer formed from a paste such as titanium oxide, zinc oxide, or copper iodide.

As a means for configuring the semiconductor material as the photoelectric conversion layer, a known method may be adopted as appropriate. For example, an about 20 nm a-Si (n layer) is formed by performing high-frequency plasma discharge in a gas in which phosphine (PH ₃ ) is added to SiH ₄ at a temperature of 200 to 500 ° C., and subsequently SiH _4. An a-Si (i layer) of about 500 nm can be formed only with gas, and then diborane (B ₂ H ₆ ) can be added to SiH ₄ to form a p-Si (p layer) of about 10 nm.

Of the pair of electrode layers sandwiching the photoelectric conversion layer, an electrode layer (hereinafter also referred to as a current collecting electrode layer) provided on the side opposite to the polyimide film substrate is formed by consolidating a conductive paste containing a conductive filler and a binder resin. The electrode layer may be a transparent electrode layer. As the transparent electrode layer, an oxide semiconductor material such as In ₂ O ₃ , SnO ₂ , ZnO, Cd ₂ SnO ₄ , ITO (In ₂ O ₃ added with Sn) can be preferably used.
Thus, a film-like solar cell in which transparent electrode / p-type a-Si / i-type a-Si / n-type a-Si / metal electrode / polyimide film are laminated in this order, which is a preferred embodiment of the present invention. can get. Alternatively, the p layer may be a-Si, the n layer may be polycrystalline silicon, and a thin undoped a-Si layer may be inserted between them. In particular, when an a-Si / polycrystalline silicon hybrid type is used, the sensitivity to the sunlight spectrum is improved. In manufacturing a solar cell, an antireflection layer, a surface protective layer, or the like may be added in addition to the above structure.

  The thin film transistor (TFT) is a semiconductor layer in which a transistor and an insulating film, an electrode, a protective insulating film, and the like constituting a transistor are formed by depositing a thin film. It is usually distinguished from silicon wafers that use silicon as the semiconductor layer. Usually, a thin film is produced by a technique using a vacuum such as PVD (physical vapor deposition) such as vacuum vapor deposition or CVD (chemical vapor deposition) such as plasma CVD. For this reason, what is not a single crystal like a silicon wafer is included. Even if Si is used, microcrystalline silicon TFT, high-temperature polysilicon TFT, low-temperature polysilicon TFT, oxide semiconductor TFT, organic semiconductor TFT, and the like are included.

  The MEMS element means an element manufactured using MEMS technology, and includes an inkjet printer head, a probe for a scanning probe microscope, a contactor for an LSI prober, an optical spatial modulator for maskless exposure, an optical integrated element, an infrared ray This includes sensors, flow sensors, acceleration sensors, MEMS gyro sensors, RF MEMS switches, internal and external blood pressure sensors, and video projectors using grating light valves and digital micromirror devices.

The sensors 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 generator, rotary encoder, optical position sensor (PSD) ), Ultrasonic distance meter, capacitance displacement meter, laser Doppler vibration speed meter, laser Doppler velocimeter,
Gyro sensor, acceleration sensor, 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 sensor, tilt sensor, vibration sensor, time sensor, and a combination of these sensors and these sensors It includes a sensor that outputs another physical quantity or sensitivity value based on some calculation formula from the value detected in.

  The logic circuit includes a logic circuit based on NAND and OR and a circuit synchronized by a clock.

Each embodiment of the method for producing a laminate of the present invention and the method for producing a device structure of the present invention described in detail above will be described with reference to the drawings as shown in FIGS.
FIG. 1 is a schematic diagram showing an embodiment of a method for producing a laminate of the present invention, where (1) shows a glass substrate 1 and (2) shows the amount of coupling agent changed on the glass substrate 1. The stage which formed the coupling agent layer 2 patterned by application | coating drying was shown. Here, in the coupling agent layer 2, a region where the amount of the coupling agent is small becomes the easy peeling portion 3, and a region where the amount of the coupling agent is large becomes the good adhesion portion 4. (3) shows the stage where the polyimide film 5 is attached, and (4) shows the stage where the polyimide film 5 ′ on the easy-peeling part 3 is cut and peeled from the glass substrate 1.
FIG. 2 is a schematic view showing an embodiment of the method for producing a device structure of the present invention, where (1) shows a glass substrate 1 and (2) shows the amount of coupling agent changed on the glass substrate 1. The step of forming a patterned coupling agent layer 2 by coating and drying is shown. Here, in the coupling agent layer 2, a region where the amount of the coupling agent is small becomes the easy peeling portion 3, and a region where the amount of the coupling agent is large becomes the good adhesion portion 4. (3) shows the stage where the polyimide film 5 is affixed, (4) shows the stage where the device 6 was subsequently fabricated on the surface of the polyimide film 5 on the easy-peeling part 3, and (5) is on the easy-peeling part 3. A stage in which the polyimide film 5 ′ is cut and peeled from the glass substrate 1 is shown.

  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.

<Reduced viscosity of polyamic acid solution>
A solution dissolved in N, N-dimethylacetamide so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube.

<Thickness of polyimide film>
The thickness of the polyimide film was measured using a micrometer (“Millitron 1245D” manufactured by FineLuf).

<Thickness unevenness of polyimide film>
The thickness unevenness of the polyimide film was obtained by randomly extracting 10 points from the film to be measured using a micrometer ("Millitron 1245D" manufactured by FineLuf), and measuring the film thickness. It calculated based on the following formula from the maximum value (maximum film thickness), the minimum value (minimum film thickness), and the average value (average film thickness).
Film thickness variation (%) = 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

<Tension modulus, tensile strength and tensile elongation at break of polyimide film>
From the polyimide film to be measured, strip-shaped test pieces each having a flow direction (MD direction) and a width direction (TD direction) of 100 mm × 10 mm were cut out, and a tensile tester (“Autograph (registered trademark)” manufactured by Shimadzu Corporation) was cut out. ); Model name AG-5000A "), and the tensile modulus, tensile strength, and tensile elongation at break were measured in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm.

<Linear expansion coefficient (CTE) of polyimide film>
About the flow direction (MD direction) and the width direction (TD direction) of the polyimide film to be measured, the expansion / contraction rate is measured under the following conditions, and intervals of 15 ° C. (30 ° C. to 45 ° C., 45 ° C. to 60 ° C., ... ) Was measured up to 300 ° C., and the average value of all measured values measured in the MD and TD directions was calculated as the coefficient of linear expansion (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 / mm ²

<Glass transition temperature>
Using a DSC differential thermal analyzer, the glass transition temperature of the polyimide film was determined from the presence or absence of heat absorption / dissipation due to structural changes in the range from room temperature to 500 ° C. No glass transition temperature was observed in any of the polyimide films.

<Evaluation of polyimide film: slipperiness>
Two polyimide films are overlapped on different surfaces (that is, not on the same surface but on the wound outer surface and the wound inner surface when wound as a film roll), and the overlapped polyimide film is sandwiched between the thumb and forefinger, The case where the polyimide film and the polyimide film slip when lightly rubbed each other was evaluated as “◯” or “good”, and the case where it did not slip was evaluated as “x” or “bad”. In addition, although it may not slip on winding outer surfaces or between winding inner surfaces, this is not made into an evaluation item.

<Evaluation of polyimide film: roll winding property>
When a long polyimide film is wound on a winding roll (outer diameter of the mandrel: 15 cm) at a speed of 2 m / min, “皺” indicates that wrinkles do not occur and smooth winding is possible. A case where wrinkles occurred partially was evaluated as “Δ”, and a case where wrinkles were generated or wound around a roll and could not be smoothly wound was evaluated as “x”.

<Evaluation of polyimide film: Degree of warpage>
From the obtained polyimide film, a 50 mm × 50 mm square was cut out to obtain a film test piece. When the film test piece is cut out, each side of the square coincides with the longitudinal direction and the width direction of the film, and the center of the square is (a) the center in the film width direction, and (b) 1 of the full width length from the left end. It was cut out from three places so as to be located at a point corresponding to / 3, and (c) a point corresponding to 1/3 of the full width from the right end.
The film test pieces (a) to (c) were left to be concave on the plane, and the distances from the four corner planes (h1, h2, h3, h4: unit mm) were measured, and the average The value was the amount of warpage (mm). The amount of warpage divided by the distance (35.36 mm) from each vertex to the center of the test piece and expressed as a percentage (%) (100 × (warp amount (mm)) / 35.36) is the degree of warpage ( %), And the degree of warpage of the film test pieces (a) to (c) was averaged.

<Evaluation of polyimide film: degree of curl>
The same film test pieces (a) to (c) used for the measurement of the degree of warpage of the polyimide film were subjected to heat treatment for 30 minutes in a 250 ° C. dry oven, and then the heat-treated film was warped in the same manner as described above. The degree of curling was defined as the degree of warpage (%) of the film after heat treatment.

<Number of craters on surface-treated polyimide film surface>
Measurement was performed by the following AFM method. That is, the number of craters on the surface of the polyimide film was measured using a scanning probe microscope with a surface property evaluation function (“SPA300 / nonavivi” manufactured by SII Nanotechnology Inc.). The measurement is performed in DFM mode, the cantilever uses “DF3” or “DF20” manufactured by SII Nanotechnology, the scanner uses “FS-20A” manufactured by SII Nanotechnology, and the scanning range is The measurement resolution was 1024 × 512 pixels. After the quadratic tilt correction was performed on the measurement image using the software attached to the apparatus, the crater portion was observed. As shown in FIG. 7, the crater has a shape in which the center of the convex portion raised from the flat portion is depressed. Therefore, the diameter of the cross section (the distance between the maximum heights) at the position of the maximum height of the swell was defined as the diameter of the crater part ((1) in FIG. It is the figure (the position where white is high, the position where black is low), (2) is a cross-sectional display example of the unevenness of the polyimide film of the white line part of (1), (3) shows the diameter of a crater part. ).

The number of craters was measured by analyzing the obtained 10 μm square measurement image (AFM image) with image processing software “ImageJ”. “ImageJ” is an open source public domain image processing software developed by the National Institutes of Health (NIH). Specifically, first, a binarization operation is performed in which a certain threshold value is used to separate a higher portion and a lower portion (see (2) and (3) in FIG. 8). At this time, as a threshold value, a position that is 12% higher than the particle size of the lubricant used from the maximum point of the distribution with respect to the information in the height direction of the AFM image (a position that is 10 nm higher when the diameter of the lubricant is 80 nm). A threshold was used. By this binarization, an image of only black and white (see (3) in FIG. 8) was obtained, and the number of ring-shaped portions therein was obtained by image processing. That is, the recognition of the annular shape is performed by performing an operation of filling the enclosed circle, and reversing the image filled in the circle (see (4) of FIG. 8) and the image not filled ((( 5) and the image logical product (see (6) in FIG. 8) can be extracted, so that only the inside of the ring can be extracted ((1) in FIG. It is the figure (the position where white is high, the position where black is low) represented by shading, (2) is a cross-sectional display example (straight line is a threshold value) of the unevenness of the polyimide film of the white line part of (1), (3) Is an example of binarization with a threshold value, (4) is an example in which the annular portion is filled, (5) is an example in which (3) is inverted, and (6) is (4) And (5)). The number of craters was calculated by counting craters with a diameter of 10 to 500 nm from the image logical product image obtained by this operation. And it measured about arbitrary three places, calculated | required the number of craters, and employ | adopted those average values.

<Thickness of coupling agent layer>
The thickness (nm) of the coupling agent layer (SC layer) is separately prepared on a cleaned Si wafer by preparing a sample obtained by applying and drying the coupling agent in the same manner as in each example and comparative example, The film thickness of the coupling agent layer formed on this Si wafer was measured by the ellipsometry method using a spectroscopic ellipsometer (“FE-5000” manufactured by Photo) under the following conditions.
Reflection angle range: 45 ° to 80 °
Wavelength range: 250 nm to 800 nm
Wavelength resolution: 1.25 nm
Spot diameter: 1mm
tan Ψ; Measurement accuracy ± 0.01
cosΔ; Measurement accuracy ± 0.01
Measurement: Method Rotating analyzer method Deflector angle: 45 °
Incident angle: 70 ° fixed Analyzer: 0-360 ° in 11.25 ° increments
Wavelength: 250 nm to 800 nm
The film thickness was calculated by fitting by a non-linear least square method. At this time, the model is Air / thin film / Si,
n = C3 / λ4 + C2 / λ2 + C1
k = C6 / λ4 + C5 / λ2 + C4
The wavelength dependence C1 to C6 was determined by the following formula.

<Peel strength>
The peel strength (180 degree peel strength) was measured under the following conditions according to the 180 degree peel method described in JIS C6471. In addition, the sample used for this measurement is provided with an unadhered portion of the polyimide film on one side by designing the size of the polyimide film to 110 mm × 2000 mm with respect to a 100 mm × 1000 mm support (glass). "Grasping."
Device name: “Autograph (registered trademark) AG-IS” manufactured by Shimadzu Corporation
Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Air Measurement sample width: 1 cm

(1) Peel strength of a good adhesion part For the measurement of the peel strength of a good adhesion part, the entire surface was a good adhesion part in the case of inkjet printing and gravure printing (the whole area was a halftone dot of a good adhesion part) Separately produced laminates were used in the same manner as in the respective examples and comparative examples except that printing was performed with an area density. When using a square-shaped stamp or a pad-shaped stamp, cut the area around the area where the silane coupling agent corresponding to the stroke is attached (good adhesion area). The peel strength of the good adhesion part was measured by peeling only the film.

(2) Peel strength of easily peelable portion In the case of ink jet printing and gravure printing, the entire surface was made to be an easily peelable portion when measuring the peel strength of the easily peelable portion (the halftone dot of the easily peelable portion). Separately produced laminates were used in the same manner as in the respective examples and comparative examples except that printing was performed with an area density. When using a square-shaped stamp or a pad-shaped stamp, avoid the area corresponding to the stroke and avoid the area where the silane coupling agent is not attached (easy peeling part). The peel strength of the easily peelable part was measured by cutting and peeling only the part.

(3) Heat-resistant peel strength The heat-resistant peel strength was measured by placing the laminate obtained by the method of each Example / Comparative Example into a muffle furnace having a nitrogen atmosphere and heating it to 400 ° C. at a temperature rising rate of 10 ° C./min. Then, after maintaining for 1 hour at 400 ° C., the laminate sample obtained by opening the door of the muffle furnace and allowing to cool in the atmosphere was used.

(4) Acid-resistant peel strength The acid-resistant peel strength was measured by immersing the laminate obtained by the method of each Example / Comparative Example in an 18% by mass hydrochloric acid solution at room temperature (23 ° C.) for 30 minutes. This was performed using a laminate sample obtained by washing with water and air drying.

(5) Alkali resistance peel strength The alkali resistance peel strength was measured by using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution (room temperature (23 ° C.)) obtained by the method of each example and comparative example. ) For 30 minutes, washed with water three times, and then air-dried, and then used a laminate sample.

<Degree of film warpage after peeling (easy peeling part)>
Cut the easy peelable part of the laminate to peel the polyimide film from the support, cut out a 50 mm x 50 mm square from the center of the peeled polyimide film to make a film test piece, and the degree of warpage of the test piece (%) Was measured in the same manner as the degree of warpage of the polyimide film, and was taken as the degree of film warp after peeling.

<Manufacture of polyimide film>
[Production Example 1-1]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, N, N-dimethylacetamide 8000 parts by mass, pyromellitic anhydride (PMDA) 530 parts by mass, paraphenylenediamine (PDA) 108 Part by mass, 204 parts by mass of orthodianiline (ODA), a dispersion obtained by dispersing colloidal silica in dimethylacetamide as a lubricant (“Snowtex (registered trademark) DMAC-ST30” manufactured by Nissan Chemical Industries) is silica (lubricant) ) Is 0.1% by mass with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture is stirred for 24 hours while maintaining the temperature at 20 ° C., and has a reduced viscosity as shown in Table 1. V1 was obtained.

(Preparation of polyimide film)
The final thickness of the polyamic acid solution V1 obtained above is applied on the smooth surface (non-sliding material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die. The film was applied so that (film thickness after imidization) was 25 μm, dried at 105 ° C. for 20 minutes, and then peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
Next, the obtained self-supporting polyamic acid film was heated stepwise in a temperature range of 150 ° C. to 420 ° C. with a pin tenter (first stage 150 ° C. × 5 minutes, second stage 250 ° C. × 10 minutes, (Third stage 420 ° C. × 5 minutes) Heat treatment was performed to imidize, and pin grip portions at both ends were dropped with a slit to obtain a long polyimide film F1 (1000 m roll) having a width of 850 mm. Table 1 shows the characteristics of the obtained film F1.

[Production Example 1-2]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and paraphenylenediamine ( (PDA) 147 parts by mass is dissolved in 4600 parts by mass of N, N-dimethylacetamide, and a dispersion obtained by dispersing colloidal silica as a lubricant in dimethylacetamide (“Snowtex (registered trademark)” manufactured by Nissan Chemical Industries, Ltd. ) DMAC-ST30 ”) was added so that the silica (lubricant) was 0.15% by mass with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture was stirred at a reaction temperature of 25 ° C. for 24 hours. A brown and viscous polyamic acid solution V2 having a reduced viscosity as shown in FIG.

(Preparation of polyimide film)
In place of the polyamic acid solution V1, the polyamic acid solution V2 obtained above was used, and the heat treatment was increased stepwise in the temperature range of 200 ° C. to 480 ° C. (first stage 200 ° C. × 5 minutes, two stages) Except that it was set to 320 ° C. × 10 minutes, 3rd stage 480 ° C. × 5 minutes), the same operation as in Production Example 1-1 was performed to obtain a long polyimide film F2 having a width of 850 mm. Table 1 shows the characteristics of the obtained film F2.

[Production Example 1-3]
(Preparation of polyamic acid solution)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), N, N-dimethylacetamide 4416 Next, a dispersion formed by dispersing colloidal silica in dimethylacetamide as a lubricant together with 217 parts by mass of pyromellitic dianhydride (PMDA) (“Snowtex” manufactured by Nissan Chemical Industries, Ltd.) (Registered trademark) DMAC-ST30 ") so that silica (lubricant) is 0.12% by mass in the total amount of polymer solids in the polyamic acid solution, and stirred for 24 hours at a reaction temperature of 25 ° C. Thus, a brown and viscous polyamic acid solution V3 having a reduced viscosity shown in Table 1 was obtained.

(Preparation of polyimide film)
A long polyimide film F3 was obtained in the same manner as in Production Example 1 except that the polyamic acid solution V3 obtained above was used instead of the polyamic acid solution V1. The properties of the obtained film F3 are shown in Table 1.

<Manufacture of plasma-treated film>
[Production Example 2-1]
One side of the polyimide film F1 obtained in Production Example 1-1 was subjected to vacuum plasma treatment to obtain a plasma-treated polyimide film P1. Table 2 shows the properties of the obtained film P1.
As the vacuum plasma processing, RIE mode using parallel plate type electrodes and RF plasma processing are adopted, nitrogen gas is introduced into the vacuum chamber, high frequency power of 13.54 MHz is introduced, and the processing time is 3 minutes.

[Production Example 2-2]
A plasma-treated polyimide film P2 was obtained in the same manner as in Production Example 2-1, except that the polyimide film F2 obtained in Production Example 1-2 was used instead of the polyimide film F1. Table 2 shows the characteristics of the obtained film P2.

[Production Example 2-3]
A plasma-treated polyimide film P3 was obtained in the same manner as in Production Example 2-1, except that the polyimide film F3 obtained in Production Example 1-3 was used instead of the polyimide film F1. Table 2 shows the properties of the obtained film P3.

[Production Example 2-4]
A plasma-treated polyimide film P4 was obtained in the same manner as in Production Example 2-3 except that the gas in the vacuum chamber was changed to oxygen gas in the vacuum plasma treatment. Table 2 shows the properties of the obtained film P4.

[Production Example 2-5]
A plasma-treated polyimide film P5 was obtained in the same manner as in Production Example 2-3 except that the gas in the vacuum chamber was changed to argon gas in the vacuum plasma treatment. Table 2 shows the properties of the obtained film P5.

<Manufacture of plasma treatment / acid treatment film>
[Production Example 3-1]
The plasma-treated film P1 obtained in Production Example 2-1 was immersed in a 10% HF aqueous solution for 1 minute, washed thoroughly with water, and then dried at 120 ° C. for 10 minutes to obtain a plasma-treated / acid-treated polyimide film T1. Obtained. Table 3 shows the characteristics of the obtained film T1. The number of craters is an average value of craters having a diameter of 10 nm to 500 nm per 100 μm ² of the film surface.

[Production Examples 3-2 to 3-5]
Plasma-treated / acid-treated polyimide in the same manner as in Production Example 3-1, except that the polyimide films P2 to P5 obtained in Production Examples 2-2 to 2-5 were used instead of the plasma-treated film P1. Films T2-T5 were obtained. Table 3 shows the characteristics of the obtained films T2 to T5. The number of craters is 10 nm to 500 n in diameter per 100 μm ² of the film surface.
The average value of m craters.

(Examples 1-1 to 1-5)
A drop-on-demand ink jet printer (manufactured by Xaar; 1001 type print head) uses a solution consisting of 1 part by mass of a silane coupling agent (“KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd.) and 99 parts by mass of isopropyl alcohol as ink. Use) on a glass (Corning EAGLE XG manufactured by Corning; 100 mm × 100 mm × 0.7 mm thickness) as a support, a dot area density of 80% (good adhesion part) with a 300 lpi screen pattern ) And a gray scale having a dot area density of 10% (easy peeling part) with a 300 lpi screen pattern. And the glass substrate after printing was put into a 100 degreeC clean oven, and it heated for 30 minutes, and formed the coupling agent layer.
Next, plasma treatment films P1 to P5 were provisionally laminated on the coupling agent layer of the obtained coupling agent-treated support using a laminator (manufactured by Climb Products) for each example. Lamination conditions were a glass temperature of 100 ° C., a roll pressure during lamination of 5 kg / cm ² , and a roll speed of 5 mm / second. The polyimide film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Then, the obtained temporary laminate laminate was put in a clean oven, heated at 200 ° C. for 30 minutes, and then allowed to cool to room temperature to obtain laminates L1 to L5 of the present invention. Table 4 shows the properties of the obtained laminate.

(Examples 1-6 to 1-10)
A sheet-fed type is a solution comprising 1.5 parts by mass of a silane coupling agent (“KBE-603” manufactured by Shin-Etsu Chemical Co., Ltd.), 90 parts by mass of isopropyl alcohol, and 8.5 parts by mass of isopropyl myristate. Using a gravure offset printing machine on a glass (Corning EAGLE XG manufactured by Corning; 100 mm × 100 mm × 0.7 mm thickness) as a support, a dot area density of 70% (good) with a screen pattern of 250 lpi A gray scale having a dot area density of 5% (easy peeling portion) was printed with a screen pattern of 250 lpi. And the glass substrate after printing was put into a 100 degreeC clean oven, and it heated for 30 minutes, and formed the coupling agent layer.
Next, plasma treatment films P1 to P5 were provisionally laminated on the coupling agent layer of the obtained coupling agent-treated support using a laminator (manufactured by Climb Products) for each example. Lamination conditions were a glass temperature of 100 ° C., a roll pressure during lamination of 5 kg / cm ² , and a roll speed of 5 mm / second. The polyimide film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Then, the obtained temporary laminate laminate was put in a clean oven, heated at 200 ° C. for 30 minutes, and then allowed to cool to room temperature to obtain laminates L6 to L10 of the present invention. Table 4 shows the properties of the obtained laminate.

(Example 2-1)
Prepare a coupling agent dilution by diluting 3-aminopropyltrimethoxysilane to 0.5% by mass with isopropyl alcohol as the silane coupling agent, and the inner side is surrounded by a square with a side of 80 mm and the outer side with a square with a side of 120 mm. After immersing the square-shaped stamp having the silicone rubber in the portion (FIG. 3 (1) shape) in the coupling agent diluent, the silane cup is placed on the substantially outer peripheral portion of the glass similar to Example 1-1. Spin on silane coupling agent dilution by pressing to ring diluent, then rotating to 3000 rpm for 15 seconds, then rotating at 3000 rpm for 15 seconds, then stopping rotation for 15 seconds The liquid was spread around the mouth shape and then dried. A cup provided with a coupling agent layer that is heated on a hot plate heated to 100 ° C. and placed on a clean bench for 1 minute, and has a thickness of 10 nm and a coupling agent applied only to the outside of the mouth shape. A ring-treated substrate was obtained.
Next, a laminate L11 of the present invention was obtained in the same manner as in Example 1-1 except that the obtained coupling agent-treated support was used.
Table 5 shows the properties of the obtained laminate.

(Example 2-2)
In Example 2-1, instead of the square-shaped stamp (the shape shown in FIG. 3 (1)), silicone rubber is applied to a portion surrounded by a square with an inner side of 80 mm and an outer side with a square of 120 mm. And a diluting solution for coupling agent using a square-shaped stamp (shape shown in FIG. 3 (2)) having a silicone rubber of 10mm width arranged to divide the central part of the inner 80mm square vertically and horizontally. Then, press the glass once onto another glass plate, and then press it onto the glass as the support to attach the coupling agent. Then, place the glass with the coupling agent in a clean oven at 100 ° C and heat for 30 minutes. Thus, a coupling agent-treated support provided with a coupling agent layer having a thickness of 50 nm and a coupling agent partially coated in a square shape was obtained.
Next, a laminate L12 of the present invention was obtained in the same manner as in Example 1-1 except that the obtained coupling agent-treated support was used.
Table 5 shows the properties of the obtained laminate.

(Comparative Example 1)
A drop-on-demand ink jet printer (manufactured by Xaar; 1001 type print head) uses a solution consisting of 1 part by mass of a silane coupling agent (“KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd.) and 99 parts by mass of isopropyl alcohol as ink. Use) on a glass (Corning EAGLE XG manufactured by Corning; 100 mm × 100 mm × 0.7 mm thickness) as a support, a dot area density of 80% (good adhesion part) with a 300 lpi screen pattern ) And a gray scale having a dot area density of 10% (easy peeling part) with a 300 lpi screen pattern. And the glass substrate after printing was put into a 100 degreeC clean oven, and it heated for 30 minutes, and formed the coupling agent layer.
Next, on the coupling agent layer of the obtained coupling agent-treated support, the polyamic acid solution V1 obtained in Production Example 1-1 as a varnish is applied with an applicator so that the dry thickness becomes about 25 μm. After coating and drying at 105 ° C. for 20 minutes, holding at 150 ° C. for 5 minutes in a dry oven, raising the temperature at 50 ° C./minute, holding at 250 ° C. for 10 minutes, and further at 50 ° C./minute A heat treatment was performed to raise the temperature and hold at 420 ° C. for 5 minutes. Then, it cooled to room temperature and obtained the laminated body L13.
Table 5 shows the properties of the obtained laminate. The peel strength of the good adhesion portion could not be measured because the film was brittle and cracked.

(Comparative Example 2)
A drop-on-demand ink jet printer (manufactured by Xaar; 1001 type print head) uses a solution consisting of 1 part by mass of a silane coupling agent (“KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd.) and 99 parts by mass of isopropyl alcohol as ink. Use) on a glass as a support (“Corning EAGLE XG” manufactured by Corning; 100 mm × 100 mm × 0.7 mm thickness), a dot pattern density of 100%, that is, complete with a screen pattern of 300 lpi Printed solid (no pattern). And the glass substrate after printing was put into a 100 degreeC clean oven, and it heated for 30 minutes, and formed the coupling agent layer.
Next, the plasma treatment / acid treatment polyimide film T1 obtained in Production Example 3-1 is subjected to the same operation as in Example 1-1 on the coupling agent layer of the obtained coupling agent-treated support. To obtain a laminate L14. Table 5 shows the properties of the obtained laminate.

(Examples 3-1 to 3-5)
Example 1 except that the plasma-treated / acid-treated polyimide films T1 to T5 obtained in Production Examples 3-1 to 3-5 were used instead of the plasma-treated film P1 used in Example 1-1. 1 to obtain laminates L15 to L19.
Table 5 shows the properties of the obtained laminate.

(Application 1)
Each laminated body obtained in Examples 1-1 to 1-5, Examples 2-1 to 2-2, Examples 3-1 to 3-5, and Comparative Example 1 was made of stainless steel having an opening. The frame was put on and fixed to the substrate holder in the sputtering apparatus. By fixing the substrate holder and the support of the laminate so that they are in close contact with each other and flowing a coolant through the substrate holder, the temperature of the laminate film can be set, and the temperature of the laminate film is set to 2 ° C. Set. First, plasma treatment was performed on the film surface. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 ⁻³ Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10 mass%) alloy target is used to form a 1 nm film by DC magnetron sputtering in an argon atmosphere. A nickel-chromium alloy film (underlayer) having a thickness of 11 nm was formed at a rate of / sec. Next, the back surface of the sputtering surface of the substrate is brought into contact with the SUS plate of the substrate holder in which a coolant whose temperature is controlled to 3 ° C. is flown, so that the temperature of the film of the laminate is set to 2 ° C., and sputtering is performed. went. Then, copper was vapor-deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.22 μm. Thus, the laminated board with a base metal thin film formation film was obtained from each laminated body. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.

Next, a laminated board with a base metal thin film forming film from each film is fixed to a Cu frame, and an electroplating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, gloss, using a copper sulfate plating bath). A thick copper plating layer (thickening layer) having a thickness of 4 μm was formed by immersing in a small amount of the agent and passing 1.5 A / dm ^{2 of} electricity. Subsequently, it was heat-treated at 120 ° C. for 10 minutes and dried to obtain a metallized polyimide film / support laminate.

After applying and drying a photoresist (“FR-200” manufactured by Shipley Co., Ltd.) to each metallized polyimide film / support laminate, the resulting metallized polyimide film / support laminate was subjected to contact exposure with a glass photomask, and further 1.2 mass% KOH. Developed with an aqueous solution. Next, etching is performed with a cupric chloride etching line containing HCl and hydrogen peroxide at a spray pressure of 40 ° C. and 2 kgf / cm ² .
A line row of line / space = 20 μm / 20 μm was formed as a test pattern. Next, after electroless tin plating was applied to a thickness of 0.5 μm, annealing treatment was performed at 125 ° C. for 1 hour. Then, the formed pattern was observed with an optical microscope, and the presence or absence of drool, pattern residue, pattern peeling, etc. was evaluated.

When the polyimide film laminated body of each Example was used, the favorable pattern without a sagging, pattern remaining, pattern peeling, etc. was obtained. Further, after the temperature is increased to 400 ° C. at a rate of temperature increase of 10 ° C./min in a muffle furnace further substituted with nitrogen, swelling and peeling occur even if the temperature is kept at 400 ° C. for 1 hour and then naturally cooled. There was nothing. Furthermore, when the razor blade is cut into the resin layer on the slightly peelable side of the boundary line between the good adhesion part and easy peelable part and the easy peelable part is peeled off, the polyimide film on which the metal pattern is formed can be peeled off without any trouble. I was able to.
On the other hand, when the laminate of Comparative Example 1 was used, the warp of the film after peeling was very large. Furthermore, when the film was bent in the opposite direction to warp, the film was cracked.

  From the results of the application example 1 described above, the laminate in which the peel strength between the support and the polyimide film is appropriately adjusted by the production method of the present invention can withstand each process such as metallization. It was confirmed that a good pattern can be formed also in pattern production.

1: Glass substrate 2: Coupling agent layer 3: Easy peeling part 4: Good adhesion part 5: Polyimide film 6: Device 10: Good adhesion part 20: Easy peeling part

Claims (10)

A method for producing a laminate of a support and a polyimide film,
A coupling agent is applied to the surface of the support opposite to the polyimide film to form a coupling agent layer, and then the support and the polyimide film are stacked and subjected to pressure and heat treatment. I mean,
In forming the coupling agent layer, a predetermined pattern comprising regions having different amounts of coupling agent is formed.   The manufacturing method of the laminated body of Claim 1 using the film which gave the plasma process previously as the said polyimide film.   The manufacturing method of the laminated body of Claim 2 using the film which gave the acid treatment after the said plasma treatment as the said polyimide film.   The application of the coupling agent is performed by at least one selected from the group consisting of inkjet printing, gravure printing, screen printing, lithographic printing, reversal printing, microcontact printing, and dispenser coating. The manufacturing method of the laminated body.   The said pressurization heat processing is a manufacturing method of the laminated body in any one of Claims 1-4 performed in an atmospheric pressure atmosphere using a roll.   The pressure heating treatment is performed separately in a pressure process and a heating process, and after pressurizing at a temperature of less than 120 ° C, heating is performed at a low pressure or a normal pressure at a temperature of 120 ° C or higher. The manufacturing method of the laminated body in any one. A laminate of a support and a polyimide film,
A laminate comprising a coupling agent layer interposed between the support and the polyimide film, wherein the coupling agent layer has a predetermined pattern composed of regions having different amounts of coupling agent.   The laminate according to claim 7, wherein the thickness unevenness of the polyimide film is 20% or less.   A method for producing a structure in which a device is formed on a polyimide film, wherein the laminate according to claim 7 or 8 having a support, a polyimide film, and a coupling agent layer is used. A method for producing a device structure, comprising: forming a device on a polyimide film, and then cutting the polyimide film in a region where the amount of the coupling agent is small to peel the polyimide film from the support. The method for manufacturing a device structure according to claim 9, comprising a step of exposing the laminated body to a high temperature of 250 ° C. or higher when forming the device.