WO2023013453A1 - Appareil d'affichage électronique - Google Patents

Appareil d'affichage électronique Download PDF

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Publication number
WO2023013453A1
WO2023013453A1 PCT/JP2022/028598 JP2022028598W WO2023013453A1 WO 2023013453 A1 WO2023013453 A1 WO 2023013453A1 JP 2022028598 W JP2022028598 W JP 2022028598W WO 2023013453 A1 WO2023013453 A1 WO 2023013453A1
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group
display device
general formula
electronic display
substituted
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PCT/JP2022/028598
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English (en)
Japanese (ja)
Inventor
桂也 ▲徳▼田
正幸 横山
郷司 前田
哲雄 奥山
治美 米虫
伝一朗 水口
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東洋紡株式会社
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Priority to JP2023540264A priority Critical patent/JPWO2023013453A1/ja
Publication of WO2023013453A1 publication Critical patent/WO2023013453A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to an electronic display device with a narrow frame, and more particularly to a type of electronic display device in which a driver IC is mounted on the back surface of the display panel.
  • the electronic display device may be simply referred to as a display device.
  • a large-area display element by tiling a screen with medium- and small-sized display elements. What is important in tiling is the width of the frame of each display element. If the frame is wide, the joints of the tiling will be conspicuous, and the charm of the large area will be lost.
  • the width of the frame depends on the arrangement of peripheral devices and parts such as display element driving circuits.
  • a drive circuit (driver IC, hereinafter also referred to as driver IC or driver element) of a display device is attached to the periphery of the display device using TAB, COF, or the like.
  • a configuration has been proposed in which a TAB or COF using a foldable film base is folded at the edge portion of the display element and a drive circuit is arranged on the side or back surface of the display element (Patent Documents 1 and 2). ). Recently, a configuration has been proposed in which the display element itself is formed on a polymer film, which is bent at the ends, and peripheral circuits and the like are arranged on the back side of the display element (Patent Documents 3 and 4).
  • an electrode formed on the display device and a terminal portion of TAB or COF are connected using ACF (anisotropic conductive film) for electrical connection with the display element.
  • ACF anisotropic conductive film
  • the present inventors have continued to study diligently, and as a result, it is possible to manufacture using existing display element manufacturing equipment, has a narrow frame, and has a high non-defective product rate for mounting the drive circuit.
  • the inventors have found a structure of a display element capable of obtaining the above, and arrived at the present invention.
  • the present invention includes the following configurations.
  • an inorganic substrate a polymer film folded to sandwich the inorganic substrate and adhered to both the first surface and the second surface of the inorganic substrate; an electronic display device formed on the surface of the polymer film bonded to the first surface of the inorganic substrate; A driving circuit element of an electronic display device mounted on the surface of the polymer film on the side bonded to the second surface of the inorganic substrate; wiring formed on the surface of the polymer film and electrically connecting the electronic display device and the drive circuit elements of the display device; including
  • the polymer film is a polyimide film that is a copolymerization reaction product of at least carboxylic acids, diamines, and silsesquioxane derivatives,
  • An electronic display device wherein the electronic device has a display section, and the external dimension Lo of the electronic display device and the external shape Ld of the display section of the electronic display device have the following relationship.
  • Lo External dimensions of the electronic display device
  • Ld External dimensions of the display portion of the electronic display device
  • Lpx Pixel dimensions of the electronic display device.
  • [4] The electronic display device according to any one of [1] to [3], wherein the polymer film and the side surface of the inorganic substrate are adhered via a silane coupling agent condensate layer. .
  • [5] The electronic display device according to any one of [1] to [4], wherein the electronic display device is a self-luminous display device.
  • [6] The electronic display device according to any one of [1] to [4], wherein the electronic display device is a reflective display device.
  • [7] The electronic display device according to any one of [1] to [6], wherein the elastic modulus of the polymer film is 7 MPa or more.
  • the present invention preferably further includes the following configurations.
  • the polymer film is characterized in that the radius of curvature of the corner of the substrate that is bent from the first surface toward the side surface is three times or less the sum of the thickness of the polymer film and the thickness of the wiring.
  • the electronic display device according to any one of [1] to [11].
  • [13] The electronic display according to any one of [1] to [12], wherein the length Lp of the polymer film parallel to the side surface of the substrate is 30% or more of the substrate thickness Ts.
  • Device [14] The electronic display device according to any one of [1] to [13], wherein the wiring has a thickness of 3 ⁇ m or less.
  • the electronic display device which is the display portion, is folded so as to sandwich the substrate, and is bonded to both the first surface and the second surface of the substrate.
  • the polymer film is adhered to a substrate, and the display portion of the electronic display device has a contour approximately equal to the substrate contour.
  • Wiring for transmitting the drive signal of the electronic display device is formed on the polymer film, and the wiring is folded along the side surface of the substrate together with the polymer film and adhered to the back side (second surface) of the substrate.
  • a drive circuit element for driving hereinafter also referred to as a driver IC is connected to the wiring on the back side of the substrate.
  • Such a display device structure has long been known for the purpose of narrowing the frame width of the display device.
  • the film that was folded was a TAB or COF base film, separate from the substrate of the electronic display device itself.
  • the display portion of the electronic display device and the lead wires arranged around the electronic display device are formed on a common polymer film substrate. Therefore, there is no terminal portion required for connection unlike TAB or COF. Therefore, since the lead wires can be bent in the vicinity of the base where the lead wires are led out from the display portion, the frame of the electronic display device can be narrowed.
  • the film can be bent at an angle close to an acute angle without damaging the wiring and the electronic display device.
  • the length Lov (1/2 x "electronic display outer dimension Lo” - “substrate outer dimension Ld") of the overhang portion where the polymer film protrudes outward from the edge of the substrate can be reduced, so that the frame can be further narrowed. becomes possible.
  • part or all of the polymer film is preferably adhered to the substrate via a condensate of a silane coupling agent.
  • the presence of the silane coupling agent condensate layer is the result of the silane coupling agent treatment.
  • the thickness of such a silane coupling agent condensate layer is extremely thin and practically negligible when compared with the thickness of the substrate and the polymer film. Therefore, since the flatness of the polymer film layer is largely controlled by the substrate, an extremely smooth surface can be obtained. This is an essential property in the formation of electronic display devices that require large-area, high-definition processing.
  • the heat resistance of the silane coupling agent condensate layer is higher than that of general adhesives made of organic substances. It can withstand a high-temperature environment in the process of forming oxide semiconductor thin films, compound semiconductor films, and the like. Furthermore, it can withstand chemical solutions, solvents, plasma processing, etc. used in processing processes such as exposure, development, etching, and resist stripping. Therefore, in the electronic display device of the present invention, the polymer film necessary for the electronic display device is directly formed on the polymer film of the laminate obtained by laminating the polymer film on the substrate with the silane coupling agent condensate layer interposed therebetween. Processing can be carried out.
  • the flexible film can be treated as if it were a single substrate, and can be processed using a conventional electronic display device manufacturing apparatus.
  • the present invention relates to a process in which a polymer precursor (a typical example is polyamic acid, which is a polyimide precursor) solution is applied onto a substrate, dried and cured to form a polymer film on the substrate. can also be applied if precise thickness control is performed.
  • the polymer film which is the substrate of the electronic display device
  • the planarity of the electronic display device is maintained.
  • the lead wiring portion bent from the periphery of the electronic display device and turned to the back of the substrate can be adhered to the back surface of the substrate together with the polymer film that is the base material.
  • the driver IC can be directly bonded to the terminals on the polymer film after adhesion.
  • the polymer film does not have a support (substrate), or when the support has low rigidity, the bonding accuracy often decreases.
  • the electronic display device of the present invention it is possible to obtain high bonding accuracy.
  • this effect is not limited to inorganic substrates, as long as substrates with flatness comparable to glass and high compressive elastic modulus are used.
  • FIG. 1A is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention.
  • polymer films are adhered to both the first surface and the second surface of the substrate via a silane coupling agent layer.
  • FIG. 1B is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention.
  • a polymer film is adhered to both the first surface and the second surface of the substrate via a silane coupling agent layer.
  • FIG. 2A is a schematic diagram showing a cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG.
  • FIG. 2(A) the first surface of the substrate and the polymer film are adhered via the silane coupling agent layer, and the second surface and the polymer film are adhered with an adhesive.
  • FIG. 2B is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG. 2(B), the first surface of the substrate and the polymer film are adhered via the silane coupling agent layer, and the second surface and the polymer film are adhered with an adhesive.
  • FIG. 3A is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG.
  • FIG. 3A the first surface of the substrate and the polymer film are adhered with an adhesive, and the second surface and the polymer film are adhered via the silane coupling agent condensate layer.
  • FIG. 3B is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG. 3(B), the first surface of the substrate and the polymer film are adhered with an adhesive, and the second surface and the polymer film are adhered via the silane coupling agent condensate layer.
  • FIG. 4 is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG.
  • FIG. 5 is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention.
  • polymer films are adhered to both the first and second surfaces of the substrate via a silane coupling agent layer.
  • the portion of the polymer film located on the side of the substrate is thinned.
  • FIG. 6 is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. The embodiment of FIG. 6 shows the case where the display portion of the electronic display device is larger than the substrate size.
  • FIG. 7 is a schematic diagram showing the cross-sectional structure of one embodiment of the electronic display device of the present invention. In the embodiment of FIG. 7, gaps exist on the sides of the substrate.
  • FIG. 8 is a diagram for explaining the first half of an example of the manufacturing process of the electronic display device of the present invention when the film lamination method is used.
  • FIG. 9A is a diagram for explaining the second half of an example of the manufacturing process of the electronic display device of the present invention when the film lamination method is used.
  • FIG. 9B is a diagram for explaining the latter half of an example of the manufacturing process of the electronic display device of the present invention when the film lamination method is used.
  • FIG. 10 is a diagram for explaining the first half of an example of the manufacturing process of the electronic display device of the present invention when the varnish method is used.
  • FIG. 14 is a schematic diagram showing details of a side portion of the electronic display device of the present invention, showing a state in which there is substantially no gap.
  • FIG. 15 is a schematic diagram showing the details of the side surface of the electronic display device of the present invention. A case of read is shown.
  • FIG. 16 is a schematic diagram showing the details of the side surface of the electronic display device of the present invention. In the case of leads, the display portion of the electronic display device has dimensions larger than the substrate dimensions.
  • FIG. 17 is a schematic diagram showing a case where a conventionally used TAB is used to mount a driver IC.
  • FIG. 18 is a schematic diagram showing the form of a side portion in an example of a conventionally proposed electronic display device.
  • FIG. 19 is a layout diagram of the simulated display device used in the embodiment of the present invention.
  • Substrate 15 is an important element that supports the entire electronic display device of the present invention.
  • Substrates include organic substrates such as polymer plates and polymer sheets, composite material substrates such as glass fiber reinforced resin substrates, inorganic filler reinforced resin substrates, carbon fiber reinforced resin substrates, glass substrates, metal substrates, metal foils, and silicon wafers. , and other inorganic substrates such as semiconductor wafers can be used.
  • a flat substrate can be used practically.
  • a flexible glass having a thickness of about several tens of micrometers can also be used as the substrate.
  • the thickness of the inorganic substrate 15 is preferably 20 ⁇ m or more, more preferably 45 ⁇ m or more, and still more preferably 300 ⁇ m or more. Also, it is preferably 5 mm or less, more preferably 1.2 mm or less, and even more preferably 0.7 mm or less. By setting the thickness of the inorganic substrate within the above range, durability and handleability are improved.
  • glass substrates include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (no alkali), and borosilicate glass. Acid glass (microsheet), aluminosilicate glass, etc.
  • these inorganic substrates preferably substrates having metals such as chromium, nickel, nichrome, molybdenum, and tungsten, and thin films such as metal oxides, metal nitrides, silicon nitride, aluminum nitride, and silicon carbide formed on the surfaces of the substrates. You can use it.
  • a metal substrate having an anodized film formed on its surface, a metal foil, or an inorganic substrate having a fluororesin coating, a silicone resin coating, or the like may be used.
  • Epoxy resin, polyimide resin, phenol resin, melamine resin, crosslinked polyester resin, polyether ether ketone resin, bismaleimide triazine resin, crosslinked acrylic resin and the like can be used as the resin for the organic substrate and the composite substrate.
  • the electronic display device of the present invention preferably has the following steps (a) to (e). (a) providing a laminate having a substrate and a polymeric film adhered to at least one side of said substrate; (b) forming an electronic display device and wiring on the polymer film; (c) removing the substrate outside the area where the electronic display device is formed, and dividing the area into a display area adhered to the substrate and a wiring area from which the substrate is removed; (d) heating the vicinity of the boundary between the display area and the wiring area to a temperature equal to or higher than the softening point of the polymer film, and bending the wiring area along the side surface of the substrate; (e) further bending the wiring region from the side surface of the substrate toward the back surface (second surface);
  • the polymer film of the present invention is used in electronic display devices.
  • the polymer film of the present invention is used for manufacturing a flexible display element, it is preferable to use a polyimide resin film having colorless transparency.
  • the flexible element refers to an element made of a polymer film with a TFT, which is used in the bottom emission type of an OLED display among electronic display devices. Since the flexible element needs to transmit light emitted from the organic EL, it is preferable to use a polyimide resin film having colorless transparency.
  • the polymer film of the present invention (hereinafter also referred to as polyimide film) is a copolymerization reaction product of at least carboxylic acids, diamines and silsesquioxane derivatives.
  • the silsesquioxane derivative has two or more dicarboxylic anhydride groups (hereinafter sometimes simply referred to as "acid anhydride groups") or two or more amino groups. These will be described below.
  • Silsesquioxane derivatives have two or more dicarboxylic anhydride groups (ie, acid anhydride groups) or two or more amino groups.
  • silsesquioxane derivatives can be copolymerized with carboxylic acids and diamines, resulting in improved toughness of polyimide films. As a result, the occurrence of cracks when the polyimide film is folded can be suppressed, and the tiling interval can be narrowed.
  • Silsesquioxane is a siloxane mainly composed of T units (for example, T8 type composed of 8 T units, T10 type composed of 10 T units, 12 T units Although it is used as a term meaning T 12 type composed of ), it may be used in a broader sense than this.
  • silsesquioxanes include not only siloxanes mainly composed of T units, but also siloxanes mainly composed of 12 or less Q units (e.g., Q 8 The term is sometimes used to denote a type, or also a Q10 type, which is composed of 10 Q units.
  • the T unit is a unit represented by RSiO 1.5 .
  • the Q unit is the unit represented by SiO2 .
  • R can represent an organic group.
  • the silsesquioxane derivative When the silsesquioxane derivative is mainly composed of T units, units other than T units, such as M units (group represented by R 3 SiO 0.5 ), D units (group represented by R 2 SiO unit), and may include the Q unit.
  • the silsesquioxane derivative is mainly composed of T units means that the number of T units is greater than the number of units other than T units (for example, the total number of M units, D units, and Q units). means a lot. Thus, for example, a silsesquioxane derivative may consist of 8 T units and 2 D units. Even when the silsesquioxane derivative is mainly composed of Q units, it may contain units other than Q units, such as M units, D units, and T units.
  • the silsesquioxane derivative is mainly composed of Q units” means that the number of Q units is greater than the number of units other than Q units (for example, the total number of M units, D units, and T units). means a lot. Also in the M unit and the D unit, R can represent an organic group.
  • the silsesquioxane derivative may have a double-decker structure, a cage structure, a random structure, or a ladder structure. It may well have a chair-type structure. Among them, a double-decker structure, a cage structure, and a random structure are preferred. A completely condensed structure (a structure containing no silanol groups) is preferred because it can suppress gelation of the polyamic acid solution. For example, a double-decker structure and a cage structure are more preferable.
  • the double-decker structure may be ring-closed or ring-opened.
  • Examples of the ring-closed double-decker structure include a structure represented by general formula AA-D1 described later and a structure represented by general formula AM-D1 described later.
  • the ring-opened double-decker structure includes, for example, a structure represented by general formula AA-D2 described later and a structure represented by general formula AM-D2 described later.
  • the cage structure may be a complete cage structure or an incomplete cage structure (for example, a corner open structure).
  • a complete cage structure is a structure in which a closed space is formed within the cage.
  • a complete cage structure is a structure in which a space is formed surrounded by six quadrangular planes having four sides composed of siloxane-bonded Si—O—Si (hereinafter, this complete cage structure is referred to as “ It is sometimes called a hexahedral perfect cage structure.).
  • the imperfect cage structure is a structure in which a space opened to the outside of the cage is formed inside the cage.
  • An example of an incomplete cage structure is a corner open structure.
  • Examples of the open-corner structure include a structure represented by general formula AA-C1 described later and a structure represented by general formula AM-C1 described later.
  • the silsesquioxane derivative can have two or more acid anhydride groups. Silsesquioxane derivatives having two or more acid anhydride groups can react with diamines.
  • the number of acid anhydride groups per molecule of the silsesquioxane derivative may be, for example, 3 or more, 4 or more, 5 or more, or 6 or more. .
  • the number of acid anhydride groups per molecule may be, for example, 10 or less, or 8 or less.
  • the silsesquioxane derivative has a cage structure or a double-decker structure
  • the number of acid anhydride groups per molecule is preferably 2 or more and 8 or less, more preferably 2, 3 or 4. .
  • the number of acid anhydride groups per molecule is preferably 2-10, more preferably 2.5-6.
  • the resulting polyimide chains are appropriately crosslinked, so that the toughness of the polyimide film can be further improved.
  • silsesquioxane derivative has two or more acid anhydride groups, it does not have two or more amino groups, which will be described later.
  • Such a silsesquioxane derivative can have, for example, a structure represented by the following general formula (hereinafter sometimes referred to as "general formula AA-D1").
  • each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted aryl group having 15 or less carbon atoms, or carbon represents a substituted or unsubstituted arylalkyl group of 15 or less
  • Q 1 is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Z 1 is each independently a structure represented by general formula (Z1-1)
  • X in general formula (Z1-1) is
  • the silsesquioxane derivative represented by general formula AA-D1 includes all geometric isomers within the scope of general formula AA-D1.
  • general formula AA-D1 where there is a geometric isomer in which a pair of Q 1 and Z 1 bonded to Si are different in the orientation of bonding to the ring plane, general formula AA-D1
  • the represented silsesquioxane derivatives include these.
  • Examples of unsubstituted alkyl groups for R 1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups. These (strictly speaking, after the propyl group) may be linear or branched.
  • a propyl group can be an n-propyl group (ie 1-propyl group) or an isopropyl group (ie 1-methylethyl group).
  • a butyl group can be an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group (ie, a 1,1-dimethylethyl group).
  • a hexyl group may be, for example, a 1,1,2-trimethylpropyl group.
  • An octyl group can be, for example, a 2,2,4-trimethylpentyl group.
  • Examples of branched unsubstituted alkyl groups include isopropyl group, isobutyl group, sec-butyl group, isooctyl group, 1,1,2-trimethylpropyl group and 2,2,4-trimethylpentyl group.
  • substituted alkyl groups include -CH 2 CH 2 CF 3 , -CH 2 CH 2 CF 2 CF 3 , -CH 2 CH 2 CF 2 CF 2 CF 3 , -CH 2 CH 2 CF 2 CF 2 CF 3 , -CH2CH2CF2CF2CF2CF3 , -CH2CH2CF2CF2CF2CF2CF3 , -CH2CH2CF ( CF3 ) 2 , -CH2 _ _ _ _ _ _ _ CH( CF3 ) , -CH( CF3 ) CH2CF2CF3 , -CH2C ( CF3 ) 2CF3 , -C( CF3 ) 2CH2CF3 , —CH2 CH 2 CF(CF 3 )CF 2 CF 3 , —CH 2 CH 2 CF(CF 3 )CF 2 CF 3 , —CH 2 CH 2 C(
  • the alkyl group for R 1 (specifically, a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms) preferably has 1 to 8 carbon atoms, such as 1, 2, 3, 4, or 8 is preferred.
  • the number of carbon atoms means the number of carbon atoms including substituents.
  • Examples of unsubstituted aryl groups for R 1 include phenyl, 1-naphthyl, 2-naphthyl and fluorenyl groups.
  • the substituted aryl group can be, for example, a group in which any number of hydrogen atoms constituting the unsubstituted aryl group described above are substituted with other atoms and/or other atomic groups.
  • an arbitrary number of hydrogen atoms constituting the above-mentioned unsubstituted aryl group is an alkyl group (specifically, a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms) It can be a substituted group. Any number of hydrogen atoms constituting the above unsubstituted aryl group may be substituted with halogen atoms.
  • substituted aryl groups include o-tolyl, m-tolyl, p-tolyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl and 4-heptyl.
  • phenyl group 4-octylphenyl group, 4-nonylphenyl group, 2,4-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 4-(1-methylethyl ) phenyl group, 4-(1,1-dimethylethyl)phenyl group, 4-(2-ethylhexyl)phenyl group, and 2,4,6-tris(1-methylethyl)phenyl group.
  • pentafluorophenyl, 4-fluorophenyl, 4-chlorophenyl and 4-bromophenyl groups can also be mentioned.
  • 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-propoxyphenyl group, 4-butoxyphenyl group, 4-pentyloxyphenyl group, 4-heptyloxyphenyl group, 4-(1-methylethoxy)phenyl group , 4-(2-methylpropoxy)phenyl group, 4-(1,1-dimethylethoxy)phenyl group, 4-ethenylphenyl group, 4-(1-methylethenyl)phenyl group, 4-(3-butenyl)phenyl Groups can also be mentioned.
  • the number of carbon atoms in the aryl group of R 1 is preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. This number of carbon atoms means the number of carbon atoms including substituents.
  • arylalkyl group for R 1 particularly unsubstituted arylalkyl group, include benzyl group and phenethyl group.
  • the substituted arylalkyl group is, for example, a group in which any number of hydrogen atoms constituting the unsubstituted arylalkyl group described above are substituted with other atoms and/or other atomic groups. can be done.
  • any number of hydrogen atoms constituting the above-mentioned unsubstituted arylalkyl group is an alkyl group (specifically, a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms) can be a group substituted with Any number of hydrogen atoms constituting the above unsubstituted arylalkyl group may be substituted with halogen atoms.
  • a fluorine atom, ie F, is preferred as the halogen atom.
  • the number of carbon atoms in the arylalkyl group of R 1 is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. This number of carbon atoms means the number of carbon atoms including substituents.
  • R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group.
  • a phenyl group is more preferable because it has interaction between aromatic rings and exhibits high heat resistance.
  • Q1 is omitted because it overlaps with the description of R1 . Therefore, the description of R 1 can also be treated as the description of Q 1 . Since there is a most preferred specific example specific to Q1 , a description of the most preferred specific example is added.
  • Q 1 is preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group, because the production difficulty is relatively low.
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • heterocyclic ring in which at least one of the carbon atoms constituting the unsubstituted aromatic ring is substituted with a hetero atom, for example, pyridine ring, pyrrole ring, furan ring, thiophene ring, thiazole ring (e.g., 1,3-thiazole ring) can be mentioned.
  • Heteroatoms include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms.
  • a heterocyclic ring in which at least one of the carbon atoms constituting the substituted aromatic ring is substituted with a hetero atom is, for example, an arbitrary number of hydrogen atoms constituting the unsubstituted heterocyclic ring having 1 to 9 carbon atoms.
  • substituted or unsubstituted, linear or branched alkyl groups Description of this alkyl group is omitted since it overlaps with the description of R 1 . Therefore, the description of R 1 can also be treated as a description of this alkyl group.
  • unsubstituted aliphatic rings having 4 to 10 carbon atoms include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornane (that is, bicyclo[2.2.1]heptane), bicyclo[2 .2.2] octane.
  • norbornane that is, bicyclo[2.2.1]heptane
  • bicyclo[2 .2.2] octane a bridged cyclic aliphatic ring such as norbornane and bicyclo[2.2.2]octane is preferable because of its relatively high thermal stability, and norbornane and bicyclo[2.2.2]octane are preferable. More preferred is norbornane.
  • the substituted aliphatic ring is, for example, a substituted or unsubstituted, straight-chain or branched alkyl group having 1 to 6 carbon atoms and any number of hydrogen atoms constituting the above-mentioned unsubstituted aliphatic ring can be a group substituted with Description of this alkyl group is omitted since it overlaps with the description of R 1 . Therefore, the description of R 1 can also be treated as a description of this alkyl group.
  • a structure in which a C atom constituting a methylene group between bridgehead atoms is substituted with an oxygen atom can be mentioned. That is, a structure in which methylene groups between bridgehead atoms of norbornane are substituted with ether bonds can be mentioned.
  • thiane and dithiane eg 1,4-dithiane
  • Heteroatoms include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms.
  • a heterocyclic ring in which at least one of the carbon atoms constituting a substituted aliphatic ring having 4 to 10 carbon atoms is substituted with a hetero atom for example, any number of hydrogen atoms constituting the above-mentioned unsubstituted heterocyclic ring , a group substituted with a substituted or unsubstituted, linear or branched alkyl group having 1 to 6 carbon atoms. Description of this alkyl group is omitted because it overlaps with the description of R 1 . Therefore, the description of R 1 can also be treated as a description of this alkyl group.
  • the number of carbon atoms in the aliphatic ring may be, for example, 6 or more, 7 or more, and 8 or more.
  • the number of carbon atoms may be 9 or less, or 8 or less. This number of carbon atoms means the number of carbon atoms including substituents.
  • rings specifically, substituted or unsubstituted aromatic rings, substituted or unsubstituted aliphatic rings having 4 to 10 carbon atoms, or at least one of the carbon atoms constituting these rings is substituted with a heteroatom.
  • condensed rings include benzofuran (eg, 1-benzofuran), benzothiophene (eg, 1-benzothiophene), and benzothiazole.
  • X is preferably a substituted or unsubstituted aromatic ring because yellowing of polyimide (for example, polyimide film) under high temperature conditions around 400°C can be further suppressed. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable. From the viewpoint of being available as a commercial product (for example, DDSQ manufactured by Japan Material Technologies Co., Ltd.), a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms is preferable, and an unsubstituted 4 to 10 carbon atom Aliphatic rings are preferred.
  • X belonging to Z 1 and Si adjacent to Z 1 may be connected with a single bond or may be connected with a connecting group.
  • the linking group that connects the two include a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, a group represented by the following structural formula (CS), an ester group ( ie ester linkages), amide groups (ie amide linkages), and combinations of any two or more thereof.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer of 0 to 8;
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene a group in which the carbon adjacent to X constituting the group) is substituted with a heteroatom,
  • the edged O is connected to Si adjacent to Z1
  • the edged Q2 is connected to X.
  • Q 2 shown at the end is connected to X means that when Q 2 shown at the end is a single bond, Si adjacent to Q 2 shown at the end is connected to X ,
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to X constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to X constituting the is substituted with a hetero atom is connected to X.
  • Linking groups include unsubstituted, linear or branched alkylene groups such as methylene, ethylene, n-propylene, n-butylene, tert-butylene, n-pentylene, n-hexylene, n -heptylene group and n-octylene group.
  • a substituted, linear or branched alkylene group can be, for example, a group in which any number of hydrogen atoms constituting the above-mentioned unsubstituted alkylene group are substituted with halogen atoms.
  • halogen atoms include fluorine atoms.
  • the number of carbon atoms in the alkylene group is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less. This number of carbon atoms means the number of carbon atoms including substituents.
  • examples of unsubstituted arylene groups include o-phenylene group, m-phenylene group, p-phenylene group, and naphthylene group (eg, 2,6-naphthylene group).
  • a substituted arylene group can be, for example, a group in which any number of hydrogen atoms constituting the above unsubstituted arylene group are substituted with an alkyl group (eg, methyl group).
  • the number of carbon atoms in the arylene group is preferably 15 or less, more preferably 12 or less, and even more preferably 7 or less. This number of carbon atoms means the number of carbon atoms including substituents.
  • Q 1 is preferably a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group.
  • n is an integer from 0 to 8. n is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less, ie, 0 or 1, for the reason that the coefficient of linear expansion (CTE) of polyimide (for example, polyimide film) can be lowered.
  • CTE coefficient of linear expansion
  • the description of the alkylene group of Q 2 (specifically, a substituted or unsubstituted, linear or branched alkylene group) is the same as the above-mentioned alkylene group (specifically Specifically, the explanation is omitted because it overlaps with the description of the substituted or unsubstituted, linear or branched alkylene group). Therefore, the above description of the alkylene group can also be treated as the description of the alkylene group of Q2 .
  • the arylene group of Q 2 (specifically, a substituted or unsubstituted arylene group) is described in connection with the above-mentioned arylene group (specifically, a substituted or unsubstituted Unsubstituted arylene group) is omitted because it overlaps with the description. Therefore, the above description of the arylene group can also be treated as the description of the arylene group of Q2 .
  • a group in which the carbon adjacent to X constituting a substituted or unsubstituted linear or branched alkylene group is substituted with a hetero atom For example, specific examples of the alkylene group described above (e.g., methylene group, ethylene group, n-propylene group, n-butylene group, tert-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, group) (specifically, the carbon adjacent to X) is substituted with a heteroatom.
  • an n-butylene group that is, a group in which the carbon adjacent to X in the tetramethylene group is substituted with a heteroatom (eg, an oxygen atom or a sulfur atom) is preferred.
  • this group that is, Q 2
  • Q 2 has 3 carbon atoms.
  • heteroatoms for Q 2 include a nitrogen atom, an oxygen atom, and a sulfur atom. Among them, an oxygen atom and a sulfur atom are preferred, and an oxygen atom is more preferred.
  • the linking group a combination of a substituted or unsubstituted arylene group and an amide group is preferable, and a combination of a p-phenylene group and an amide group is more preferable.
  • the following structures are preferred. Note that the structural formula below indicates that the p-phenylene group is bonded to Si.
  • An amide group indicates that it is attached to X. That is, it indicates that the carbon constituting the amide group is bonded to X.
  • Z1 preferably has the following structure.
  • Both are preferably connected by a single bond. This is because the yellowing of polyimide (for example, a polyimide film) under high temperature conditions can be further suppressed by connecting the two with a single bond.
  • polyimide for example, a polyimide film
  • the structure represented by general formula (Z1-1) is preferably the following structure. That is, when both are linked by a single bond, Z 1 preferably has the following structure.
  • the silsesquioxane derivative represented by the general formula AA-D1 is, for example, JP-A-2004-331647 (the corresponding patent publication is Japanese Patent No. 448334), JP-A-2006-265243. (The corresponding patent publication is Japanese Patent No. 5082258), JP 2007-302635 (the corresponding patent publication is Japanese Patent No. 4946169), the method described in WO2003/024870. can be manufactured according to
  • silsesquioxane derivative represented by the general formula AA-D1 can be produced by reacting a compound having an SiH group) with a compound having an acid anhydride group.
  • This reaction can utilize, for example, hydrosilylation. That is, it is possible to utilize a reaction in which a compound having a SiH group is added to an unsaturated bond such as a carbon-carbon double bond, accompanied by breaking of the Si—H bond.
  • compounds having anhydride groups can have unsaturated bonds (eg, vinyl groups) such as carbon-carbon double bonds.
  • unsaturated bonds eg, vinyl groups
  • a coupling reaction specifically, a compound having a SiH group using a noble metal catalyst such as ruthenium, platinum, palladium, rhodium, etc. and a coupling reaction with an aryl halide can also be used.
  • a compound having an acid anhydride group or a compound having a functional group convertible to an acid anhydride group can have an aryl halide structure. Examples of functional groups convertible to acid anhydride groups include diester groups.
  • silsesquioxane derivatives represented by the general formula AA-D1 for example, the following silsesquioxane derivatives are available as commercial products (for example, DDSQ manufactured by Japan Material Technology Co., Ltd.).
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as "general formula AA-D2").
  • each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Z 1 are each independent, at least two of Z 1 have a structure represented by general formula (Z1-1);
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least one of the carbon atoms constituting these rings is a hetero atom.
  • Z 1 that is not a structure represented by general formula (Z1-1) exists, Z 1 that is not a structure is H or a structure represented by general formula (Z1-S), Q S1 in general formula (Z1-S) is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; It represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms.
  • the silsesquioxane derivative represented by general formula AA-D2 includes all geometric isomers within the range of general formula AA-D2.
  • a geometric isomer represented by the general formula AA-D2 there is a geometric isomer in which the pair of R 1 and OZ 1 bound to Si are different in the orientation of bonding to the ring plane, and the general formula AA- Silsesquioxane derivatives represented by D2 include these.
  • R 1 in general formula AA-D2 is omitted because it duplicates the description of R 1 in general formula AA-D1. Therefore, the description of R 1 of general formula AA-D1 can also be treated as the description of R 1 of general formula AA-D2. Therefore, for example, R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group, more preferably a phenyl group.
  • At least two of Z 1 are structures represented by general formula (Z1-1). That is, two of the four Z 1 may have a structure represented by the general formula (Z1-1), three may have a structure represented by the general formula (Z1-1), and four One may be a structure represented by general formula (Z1-1).
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of X in general formula (Z1-1) in general formula AA-D2 is omitted because it duplicates the description of X in general formula (Z1-1) in general formula AA-D1.
  • X of general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of X of general formula (Z1-1) in general formula AA-D2. Therefore, for example, X is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects X belonging to Z 1 and O adjacent to Z 1 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene a group in which the carbon adjacent to X constituting the group) is substituted with a heteroatom
  • the edged Si is connected to O adjacent to Z1
  • the edged Q2 is connected to X.
  • Q 2 shown at the end is connected to X means that when Q 2 shown at the end is a single bond, Si adjacent to Q 2 shown at the end is connected to X ,
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to X constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to X constituting the is substituted with a hetero atom is connected to X.
  • the linking group is a substituted or unsubstituted, linear or branched alkylene group
  • the description of the alkylene group as the linking group refers to the alkylene group of general formula AA-D1 (specifically, a substituted or unsubstituted , straight-chain or branched alkylene group) are omitted here. Therefore, the description of the alkylene group of general formula AA-D1 can also be treated as the description of this alkylene group (that is, the alkylene group of general formula AA-D2).
  • the description of the arylene group as the linking group is the same as the description of the arylene group of general formula AA-D1 (specifically, the substituted or unsubstituted arylene group). Omitted due to duplication. Therefore, the description of the arylene group of general formula AA-D1 can also be treated as the description of this arylene group (that is, the arylene group of general formula AA-D2).
  • Q 1 is preferably a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group.
  • n is an integer from 0 to 8. n is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less, ie, 0 or 1, for the reason that the coefficient of linear expansion (CTE) of polyimide (for example, polyimide film) can be lowered.
  • CTE coefficient of linear expansion
  • the alkylene group of Q 2 (specifically, a substituted or unsubstituted, linear or branched alkylene group) is the alkylene group of general formula AA-D1 (Specifically, a substituted or unsubstituted, straight-chain or branched alkylene group) is omitted because it duplicates the description. Therefore, the description of the alkylene group of general formula AA-D1 can also be treated as the description of the alkylene group of Q2 .
  • the arylene group of Q 2 (specifically, a substituted or unsubstituted arylene group) is the arylene group of general formula AA-D1 (specifically, (Substituted or unsubstituted arylene group). Therefore, the description of the arylene group of general formula AA-D1 can also be treated as the description of the arylene group of Q2 .
  • a group in which the carbon adjacent to X constituting a substituted or unsubstituted linear or branched alkylene group is substituted with a hetero atom for example, Specific examples of alkylene groups exemplified by general formula AA-D1 (for example, methylene group, ethylene group, n-propylene group, n-butylene group, tert-butylene group, n-pentylene group, n-hexylene group, n-heptylene group , n-octylene group) (specifically, the carbon adjacent to X) is substituted with a heteroatom.
  • alkylene groups exemplified by general formula AA-D1 for example, methylene group, ethylene group, n-propylene group, n-butylene group, tert-butylene group, n-pentylene group, n-hexylene group, n-heptylene group , n-octylene group
  • an n-butylene group that is, a group in which the carbon adjacent to X in the tetramethylene group is substituted with a heteroatom (eg, an oxygen atom or a sulfur atom) is preferred.
  • this group that is, Q 2
  • Q 2 has 3 carbon atoms.
  • heteroatoms for Q2 include a nitrogen atom, an oxygen atom, and a sulfur atom. Among them, an oxygen atom and a sulfur atom are preferred, and an oxygen atom is more preferred.
  • a carbonyl group is preferred as the linking group.
  • the structure represented by general formula (Z1-1) is preferably the following structure. That is, when the linking group is a carbonyl group, Z 1 preferably has the following structure.
  • Z 1 that is not a structure represented by general formula (Z1-1) is H, that is, a hydrogen atom, or a structure represented by general formula (Z1-S). If Z1 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z1-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Q S1 in general formula (Z1-S), the explanation of Q S1 overlaps with the explanation of R 1 , so it is omitted. Thus, the description of R1 can also be treated as the description of QS1 . Since there is a preferred embodiment specific to Q S1 , a description of the preferred embodiment is added.
  • QS1 is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of raw material availability.
  • the silsesquioxane derivative represented by the general formula AA-D2 is produced, for example, based on the method described in the literature listed in the explanation of the production of the silsesquioxane derivative represented by the general formula AA-D1. can do.
  • a compound in which all Z 1 in general formula AA-D2 is a hydrogen atom or a sodium atom is prepared, and this compound (that is, a silanol group containing H or Na as Z 1 and O adjacent to Z 1
  • a silsesquioxane derivative represented by the general formula AA-D1 can also be produced by a ring-closing reaction (endcapping reaction) between a dichlorosilane derivative having an acid anhydride group and a compound having
  • a compound in which all Z 1 in general formula AA-D2 is a hydrogen atom or a sodium atom is prepared, and the compound (i.e., H or Na as Z 1 and a silanol group containing O adjacent to Z 1 is compound) with an organochlorosilane having a SiH group, such as dimethylchlorosilane, and reacting the product (i.e., the product having a SiH group) with a compound having an anhydride group.
  • an organochlorosilane having a SiH group such as dimethylchlorosilane
  • silanol groups i.e. compounds with silanol groups containing H as Z 1 and O adjacent to Z 1
  • acid chlorides with an anhydride group such as trimellitic anhydride chloride or the reaction with diorganochlorosilane having SiH groups
  • some of the silanol groups may be capped.
  • compounds with silanol groups can be reacted with, for example, triorganochlorosilanes such as triphenylchlorosilane.
  • Hydrosilylation for example, can be used to react a product having SiH groups with a compound having an anhydride group.
  • a reaction can be used in which a product having SiH groups adds to an unsaturated bond such as a carbon-carbon double bond, with the breaking of the Si—H bond.
  • compounds having anhydride groups can have unsaturated bonds (eg, vinyl groups) such as carbon-carbon double bonds.
  • a coupling reaction specifically, a reaction having a SiH group using a noble metal catalyst such as ruthenium, platinum, palladium, rhodium, etc.
  • a coupling reaction between the product and an aryl halide can also be used.
  • a compound having an acid anhydride group or a compound having a functional group convertible to an acid anhydride group can have an aryl halide structure. Examples of functional groups convertible to acid anhydride groups include diester groups.
  • this explanation (specifically, the explanation of the production of the silsesquioxane derivative represented by the general formula AA-D2, including the explanation of various reactions) It can also be appropriately treated as a description for producing a silsesquioxane derivative of the structure.
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as "general formula AA-C1").
  • each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Z 1 are each independent, at least two of Z 1 have a structure represented by general formula (Z1-1)
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least one of the carbon atoms constituting these rings is a hetero atom.
  • Z 1 that is not a structure represented by general formula (Z1-1) exists, Z 1 that is not a structure is H or a structure represented by general formula (Z1-S), Q S1 in general formula (Z1-S) is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; It represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms.
  • the silsesquioxane derivative represented by general formula AA-C1 includes all geometric isomers within the range of general formula AA-C1.
  • a geometric isomer represented by the general formula AA-C1 there is a geometric isomer in which a pair of R 1 and OZ 1 bonded to Si are different in the orientation of bonding to the ring plane.
  • Silsesquioxane derivatives represented by C1 include these.
  • R 1 in general formula AA-C1 is omitted because it duplicates the description of R 1 in general formula AA-D1. Therefore, the description of R 1 of general formula AA-D1 can also be treated as the description of R 1 of general formula AA-C1. Therefore, for example, R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group, more preferably a phenyl group.
  • At least two of Z 1 are structures represented by general formula (Z1-1). That is, two of the three Z 1 may have structures represented by general formula (Z1-1), and three may have structures represented by general formula (Z1-1).
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of X in general formula (Z1-1) in general formula AA-C1 is omitted because it duplicates the description of X in general formula (Z1-1) in general formula AA-D1.
  • X of general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of X of general formula (Z1-1) in general formula AA-C1. Therefore, for example, X is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects X belonging to Z 1 and O adjacent to Z 1 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene a group in which the carbon adjacent to X constituting the group) is substituted with a heteroatom
  • the edged Si is connected to O adjacent to Z1
  • the edged Q2 is connected to X.
  • linking group is omitted since it overlaps with the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula AA-C1. Therefore, for example, a carbonyl group is preferable as the linking group.
  • the linking group is a carbonyl group
  • the structure represented by general formula (Z1-1) is preferably the following structure. That is, when the linking group is a carbonyl group, Z 1 preferably has the following structure.
  • Z 1 that is not a structure represented by general formula (Z1-1) is H, that is, a hydrogen atom, or a structure represented by general formula (Z1-S). If Z1 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z1-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Z1-S For a specific combination of three Z 1 s , it is preferred that two Z 1 's have the following structures and one has a structure represented by the general formula (Z1-S).
  • Silsesquioxane derivatives of general formula AA-C1 can be prepared, for example, by the procedure described for general formula AA-D2, except for preparing compounds in which all Z 1 in general formula AA-C1 are hydrogen atoms. can be manufactured in a similar manner.
  • Compounds in which all Z 1 in general formula AA-C1 are hydrogen atoms can be produced, for example, according to the method described in the following literature. Chemistry Letters, 2014, Vol. 43, No. 10, pp. 1532-1534
  • compounds in which all Z 1 are hydrogen atoms can also be obtained as commercial products (for example, SO1450 and SO1458 manufactured by Hybrid Plastics).
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as "general formula AA-Q1").
  • Z 1 is independently At least two of Z 1 have a structure represented by general formula (Z1-1)
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring having 4 to 10 carbon atoms, A substituted or unsubstituted aliphatic ring, a heterocyclic ring in which at least one of the carbon atoms constituting these rings is substituted with a heteroatom, or a ring in which at least two of these are condensed, X belonging to Z 1 and O adjacent to Z 1 are linked by a linking group
  • Z 1 that is not a structure represented by general formula (Z1-1) exists
  • Z 1 that is not a structure is H or a structure represented by general formula (Z1-S)
  • Q S1 in general formula (Z1-S) is each independently
  • At least two of Z 1 are structures represented by general formula (Z1-1). Although all eight Z 1 may have this structure, it is preferable that two to six of the eight Z 1 have this structure, more preferably two to four have this structure, and two or three are more preferably this structure.
  • X in general formula (Z1-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of X in general formula (Z1-1) in general formula AA-Q1 is omitted because it duplicates the description of X in general formula (Z1-1) in general formula AA-D1.
  • X of general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of X of general formula (Z1-1) in general formula AA-Q1. Therefore, for example, X is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects X belonging to Z 1 and O adjacent to Z 1 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • Q 2 shown at the end is connected to X means that when Q 2 shown at the end is a single bond, Si adjacent to Q 2 shown at the end is connected to X ,
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to X constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to X constituting the is substituted with a hetero atom is connected to X.
  • linking group Description of the linking group is omitted because it overlaps with the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula AA-Q1.
  • Z 1 that is not a structure represented by general formula (Z1-1) is H, that is, a hydrogen atom, or a structure represented by general formula (Z1-S). If Z1 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z1-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Q S1 in general formula (Z1-S) the explanation of Q S1 is omitted since it overlaps with the explanation of R 1 in general formula AA-D1. Therefore, the description of R 1 in general formula AA-D1 can also be treated as the description of Q S1 . Since there is a preferred embodiment specific to Q S1 , a description of the preferred embodiment is added.
  • QS1 is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of raw material availability.
  • Silsesquioxane derivatives of general formula AA-Q1 can be prepared, for example, by the procedure described for general formula AA-D2, except to prepare compounds in which all Z 1 in general formula AA-Q1 are hydrogen atoms. can be manufactured in a similar manner.
  • a compound in which all Z 1 are hydrogen atoms in the general formula AA-Q1 can be obtained by, for example, preparing a tetramethylammonium salt corresponding to a compound in which all Z 1 are hydrogen atoms, based on the method described in the following literature: It can be produced by protonation with an acid. Chemistry Letters, 2018, Vol. 47, No. 12, pp. 1530-1533
  • a tetramethylammonium salt corresponding to a compound in which all Z 1 in general formula AA-Q1 are hydrogen atoms is also available as a commercial product (for example, Hybrid Plastics MS0860).
  • silsesquioxane derivatives with random structures Examples of silsesquioxane derivatives with random structures will be described later.
  • the silsesquioxane derivative can have two or more amino groups. If the silsesquioxane derivative has two or more amino groups, it can be reacted with carboxylic acids.
  • the number of amino groups per molecule of the silsesquioxane derivative may be, for example, 3 or more, 4 or more, 5 or more, or 6 or more.
  • the number of amino groups per molecule may be, for example, 10 or less, or 8 or less.
  • the number of amino groups per molecule is preferably 2 or more and 8 or less.
  • the number of amino groups per molecule is preferably 2-10, more preferably 2.5-6.
  • the resulting polyimide chains are appropriately crosslinked, so that the toughness of the polyimide film can be further improved.
  • silsesquioxane derivative When the silsesquioxane derivative has two or more amino groups, it does not have two or more acid anhydride groups.
  • Each amino group preferably has a linking group that links the amino group to the Si that is closest to the amino group in terms of bonding among the Si that constitutes the silsesquioxane derivative. Since the linking group will be described in detail in the silsesquioxane derivative represented by the general formula AM-D1 described later, only a brief description will be given here for the purpose of avoiding duplication. Examples of the linking group include structures described for Z 2 in general formula AM-D1 described later.
  • linking group that links both (the amino group and the Si constituting the silsesquioxane derivative, which is closest to the amino group in terms of bonding), for example, a substituted or unsubstituted, linear or A branched alkylene group, a substituted or unsubstituted arylene group, a group represented by the structural formula (CS) described later, an ester group (that is, an ester bond), an amide group (that is, an amide bond), and any two thereof One or more combinations can be mentioned.
  • the amino group is bound to the ring represented by Y (see general formula AM-D1 described below)
  • the linking group further has a ring represented by Y. be able to.
  • the linking group is a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, a group represented by the structural formula (C—S) described later, an ester group. (that is, ester bond), an amide group (that is, amide bond), or any combination of two or more thereof, and further has a ring represented by Y.
  • Y is a substituted or unsubstituted aromatic ring
  • an amino group can be attached to the substituted or unsubstituted aromatic ring.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • the silsesquioxane derivative can have, for example, a structure represented by the following general formula (hereinafter sometimes referred to as "general formula AM-D1").
  • general formula AM-D1 a structure represented by the following general formula (hereinafter sometimes referred to as "general formula AM-D1").
  • each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Q 1 is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon
  • Y belonging to Z 2 and Si adjacent to Z 2 may be connected by a single bond or may be connected by a connecting group,
  • the amino group belonging to general formula (Z2-2) and Si adjacent to Z2 are linked by a linking group.
  • the silsesquioxane derivative represented by general formula AM-D1 includes all geometric isomers within the range of general formula AM-D1.
  • a geometric isomer represented by the general formula AM-D1 there is a geometric isomer in which a pair of Q 1 and Z 2 bonded to Si are different in the orientation of bonding to the ring plane, in the general formula AM-D1
  • the represented silsesquioxane derivatives include these.
  • R 1 in general formula AM-D1 is omitted because it duplicates the description of R 1 in general formula AA-D1. Therefore, the description of R 1 of general formula AA-D1 can also be treated as the description of R 1 of general formula AM-D1. Therefore, for example, R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group, more preferably a phenyl group.
  • Q1 is omitted because it overlaps with the description of R1 . Therefore, the description of R 1 can also be treated as the description of Q 1 . Since there is a most preferred specific example specific to Q1 , a description of the most preferred specific example is added.
  • Q 1 is preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group, because the production difficulty is relatively low.
  • Y is preferably a substituted or unsubstituted aromatic ring because, for example, yellowing of polyimide (for example, polyimide film) under high temperature conditions can be further suppressed. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • Y belonging to Z 2 and Si adjacent to Z 2 may be connected with a single bond or may be connected with a connecting group.
  • the linking group that connects the two include a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, a group represented by the following structural formula (CS), an ester group ( ie ester linkages), amide groups (ie amide linkages), and combinations of any two or more thereof.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene a group in which the carbon adjacent to Y constituting the group) is substituted with a heteroatom
  • the O shown on the edge is connected to Si adjacent to Z2
  • the Q2 shown on the edge is connected to Y.
  • Q 2 shown at the end is connected to Y means that Si adjacent to Q 2 shown at the end is connected to Y when Q 2 shown at the end is a single bond.
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to Y constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to Y constituting
  • linking group in general formula AM-D1 is omitted because it overlaps with the description of the linking group in general formula AA-D1. Therefore, the description of the linking group in general formula AA-D1 can also be treated as the description of the linking group in general formula AM-D1.
  • the linking group is preferably a combination of a substituted or unsubstituted arylene group and an amide group, and more preferably a combination of a p-phenylene group and an amide group.
  • the following structures are preferred. Note that the structural formula below indicates that the p-phenylene group is bonded to Si. It shows that the amide group is attached to Y. That is, it indicates that the carbon constituting the amide group is bonded to Y.
  • Z2 When both (that is, Y belonging to Z2 and Si adjacent to Z2 ) are linked by this linking group, Z2 preferably has the following structure.
  • the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • Both are preferably connected by a single bond. This is because the yellowing of polyimide (for example, polyimide film) under high-temperature conditions can be further suppressed by connecting the two with a single bond.
  • polyimide for example, polyimide film
  • the structure represented by general formula (Z2-1) is preferably the following structure. That is, when both are linked by a single bond, Z2 preferably has the following structure.
  • the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred. That is, Z 2 more preferably has the following structure.
  • the amino group belonging to general formula (Z2-2) and Si adjacent to Z 2 are linked by a linking group.
  • the linking group that links the two include a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, a group represented by the above structural formula (C—S), an ester group ( ie ester linkages), amide groups (ie amide linkages), and combinations of any two or more thereof.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • linking group of general formula (Z2-2) in general formula AM-D1 is omitted because it overlaps with the description of the linking group of general formula AA-D1. Therefore, the description of the linking group in general formula AA-D1 can also be treated as the description of the linking group of general formula (Z2-2) in general formula AM-D1. Since there is a most preferred specific example unique to the linking group of general formula (Z2-2) in general formula AM-D1, the description of the most preferred specific example will be added.
  • the linking group of general formula (Z2-2) in general formula AM-D1 is a substituted or unsubstituted, linear or branched alkylene group for the reason that the production difficulty is relatively low. An unsubstituted straight-chain alkylene group having 6 or less carbon atoms is preferred, and an n-propylene group, that is, a trimethylene group is even more preferred.
  • Both of Z 2 are structures represented by general formula (Z2-1), or both of Z 2 are structures represented by general formula (Z2-2) preferable.
  • the silsesquioxane derivative represented by the general formula AM-D1 is produced, for example, based on the method described in the literature listed in the explanation of the production of the silsesquioxane derivative represented by the general formula AA-D1. can do. For example, it can be produced in the same procedure as described for general formula AA-D1, except that a compound having an amino group is used instead of a compound having an acid anhydride group. In addition, in the compound having an amino group, the amino group may be protected.
  • silsesquioxane derivatives represented by the general formula AM-D1 the following silsesquioxane derivatives used in Examples described later are described as being produced in JP-A-2006-265243. ing.
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as "general formula AM-D2").
  • general formula AM-D2 wherein each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Z 2 are each independent, at least two of Z 2 have a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2);
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least one of the carbon atoms constituting these rings is a hetero atom.
  • Z 2 that is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2)
  • Z 2 that is not such a structure is H
  • general formula (Z2- S) is a structure represented by Q S1 in general formula (Z2-S) is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; It represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms.
  • the silsesquioxane derivative represented by general formula AM-D2 includes all geometric isomers within the range of general formula AM-D2.
  • a geometric isomer represented by general formula AM-D2 there exists a geometric isomer in which a pair of R 1 and OZ 2 bonded to Si are different in the orientation of bonding to the ring plane.
  • Silsesquioxane derivatives represented by D2 include these.
  • R 1 in general formula AM-D2 is omitted because it duplicates the description of R 1 in general formula AA-D1. Therefore, the description of R 1 of general formula AA-D1 can also be treated as the description of R 1 of general formula AM-D2. Therefore, for example, R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group, more preferably a phenyl group.
  • At least two of Z 2 are each independently a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2). That is, two of the four Z 2 may each independently be a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2), and three of which are Each independently may be a structure represented by the general formula (Z2-1) or a structure represented by the general formula (Z2-2), and each of the four may be independently represented by the general formula (Z2- 1) or a structure represented by general formula (Z2-2).
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of Y in general formula (Z2-1) in general formula AM-D2 is omitted because it duplicates description of X in general formula (Z1-1) in general formula AA-D1. Therefore, the explanation of X in general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of Y in general formula (Z2-1) in general formula AM-D2.
  • X is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects Y belonging to Z 2 and O adjacent to Z 2 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched A group in which the carbon adjacent to Y constituting the alkylene group) is substituted with a hetero atom, Si shown at the edge is connected to O adjacent to Z2 , and Q2 shown at the edge is connected to Y.
  • Q2 shown at the end is connected to Y means that Si adjacent to Q2 shown at the end is connected to Y when Q2 shown at the end is a single bond.
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to Y constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to Y constituting
  • a carbonyl group is preferable as the linking group.
  • the structure represented by general formula (Z2-1) is preferably the following structure. That is, when the linking group is a carbonyl group, Z2 preferably has the following structure. In this structure, the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • a group represented by structural formula (C) is also preferred.
  • Z 2 preferably has the following structure. In this structure, the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • linking group of general formula (Z2-1) should be given as the linking group linking the amino group belonging to general formula (Z2-2) and O adjacent to Z 2 .
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • linking group of general formula (Z2-2) in general formula AM-D2 is omitted because it duplicates the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula (Z2-2) in general formula AM-D2. Therefore, for example, groups represented by Structural Formula (C) are preferred.
  • Z 2 preferably has the following structure.
  • Z 2 which is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2), is H, that is, a hydrogen atom, or a structure represented by general formula (Z2-S) is. If Z2 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z2-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Q S1 in general formula (Z2-S), the explanation of Q S1 overlaps with the explanation of R 1 , so it is omitted. Thus, the description of R1 can also be treated as the description of QS1 . Since there is a preferred embodiment specific to Q S1 , a description of the preferred embodiment is added.
  • QS1 is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of raw material availability.
  • all four Z 2 have a structure represented by general formula (Z2-1), or all four Z 2 have a structure represented by general formula (Z2- The structure represented by 2) is preferable.
  • silsesquioxane derivative represented by general formula AM-D2 is the same procedure as described for general formula AA-D2 except that a compound having an amino group is used instead of a compound having an acid anhydride group. It can be manufactured by such a procedure. In addition, in the compound having an amino group, the amino group may be protected.
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as “general formula AM-C1”).
  • general formula AM-C1 wherein each R 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms
  • Z 2 are each independent, at least two of Z 2 are each independently a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2);
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least one of the carbon atoms constituting these rings is a hetero atom.
  • Z 2 that is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2)
  • Z 2 that is not such a structure is H
  • general formula (Z2- S) is a structure represented by Q S1 in general formula (Z2-S) each independently represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; It represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms.
  • the silsesquioxane derivative represented by general formula AM-C1 includes all geometric isomers within the scope of general formula AM-C1.
  • a geometric isomer represented by the general formula AM-C1 there is a geometric isomer in which a pair of R 1 and OZ 2 bonded to Si are different in the orientation of bonding to the ring plane.
  • Silsesquioxane derivatives represented by C1 include these.
  • R 1 in general formula AM-C1 is omitted because it duplicates the description of R 1 in general formula AA-D1. Therefore, the description of R 1 of general formula AA-D1 can also be treated as the description of R 1 of general formula AM-C1. Therefore, for example, R 1 is preferably a methyl group, an ethyl group, an isobutyl group, an isooctyl group, a trifluoropropyl group or a phenyl group, more preferably a phenyl group.
  • At least two of Z 2 are each independently a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2). That is, two of the three Z 2 may independently be a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2), and three of which are Each independently may be a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2).
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of Y in general formula (Z2-1) in general formula AM-C1 is omitted because it duplicates the description of X in general formula (Z1-1) in general formula AA-D1. Therefore, the explanation of X in general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of Y in general formula (Z2-1) in general formula AM-C1.
  • Y is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions of, for example, around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects Y belonging to Z 2 and O adjacent to Z 2 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene group) is a group in which the carbon adjacent to Y is substituted with a heteroatom,
  • the Si shown at the edge is connected to O adjacent to Z2
  • the Q2 shown at the edge is connected to Y.
  • Q 2 shown at the end is connected to Y means that Si adjacent to Q 2 shown at the end is connected to Y when Q 2 shown at the end is a single bond.
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to Y constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to Y constituting
  • linking group is omitted because it overlaps with the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula AM-C1. Therefore, for example, a carbonyl group is preferable as the linking group.
  • the structure represented by general formula (Z2-1) is preferably the following structure. That is, when the linking group is a carbonyl group, Z2 preferably has the following structure. In this structure, the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • a group represented by structural formula (C) is also preferred.
  • Z 2 preferably has the following structure. In this structure, the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • linking group of general formula (Z2-1) should be given as the linking group linking the amino group belonging to general formula (Z2-2) and the O adjacent to Z 2 .
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • linking group of general formula (Z2-2) in general formula AM-C1 is omitted because it overlaps with the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula (Z2-2) in general formula AM-C1. Therefore, for example, groups represented by Structural Formula (C) are preferred.
  • Z 2 preferably has the following structure.
  • At least two of Z 2 are preferably structures represented by general formula (Z2-1), or at least two of Z 2 are preferably structures represented by general formula (Z2-2).
  • Z 2 which is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2), is H, that is, a hydrogen atom, or a structure represented by general formula (Z2-S) is. If Z2 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z2-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Q S1 in general formula (Z2-S), the explanation of Q S1 overlaps with the explanation of R 1 , so it is omitted. Thus, the description of R1 can also be treated as the description of QS1 . Since there is a preferred embodiment specific to Q S1 , a description of the preferred embodiment is added.
  • QS1 is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of raw material availability.
  • Z2-S a structure represented by the general formula (Z2-S).
  • the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • Z2 two of Z 2 have the structures below and one has a structure represented by general formula (Z2-S).
  • Z2-S general formula
  • the position of the amino group may be the ortho position, the meta position, or the para position. Among them, the para position is preferred.
  • Z2-S a structure represented by general formula (Z2-S).
  • silsesquioxane derivative represented by general formula AM-C1 is the same procedure as described for general formula AA-C1 except that a compound having an amino group is used instead of a compound having an acid anhydride group. It can be manufactured by such a procedure. In addition, in the compound having an amino group, the amino group may be protected.
  • the silsesquioxane derivative can also have a structure represented by, for example, the following general formula (hereinafter sometimes referred to as “general formula AM-Q1”).
  • general formula AM-Q1 a structure represented by, for example, the following general formula (hereinafter sometimes referred to as “general formula AM-Q1”).
  • Z 2 are each independently at least two of Z 2 are each independently a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2);
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least one of the carbon atoms constituting these rings is a hetero atom.
  • Z 2 that is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2)
  • Z 2 that is not such a structure is H
  • general formula (Z2- S) is a structure represented by Q S1 in general formula (Z2-S) is each independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; It represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms.
  • At least two of Z 2 are each independently a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2). All eight Z 2 may each independently be a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2), but Z 2 out of eight , two to six may each independently be a structure represented by general formula (Z2-1) or a structure represented by general formula (Z2-2), and two to four of Each independently may be a structure represented by the general formula (Z2-1) or a structure represented by the general formula (Z2-2), and two or three may each independently be a structure represented by the general formula It may be a structure represented by (Z2-1) or a structure represented by general formula (Z2-2).
  • Y in general formula (Z2-1) is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms, and at least A heterocyclic ring in which one is substituted with a heteroatom, or a ring in which at least two of these are fused.
  • Description of Y in general formula (Z2-1) in general formula AM-Q1 is omitted because it duplicates the description of X in general formula (Z1-1) in general formula AA-D1. Therefore, the explanation of X in general formula (Z1-1) in general formula AA-D1 can also be treated as the explanation of Y in general formula (Z2-1) in general formula AM-Q1.
  • Y is preferably a substituted or unsubstituted aromatic ring because it can further suppress yellowing of polyimide (for example, polyimide film) under high temperature conditions, for example, around 400°C. Considering the difficulty of production, an unsubstituted aromatic ring is more preferable.
  • linking group that connects Y belonging to Z 2 and O adjacent to Z 2 , for example, a substituted or unsubstituted linear or branched alkylene group, a carbonyl group, a substituted or unsubstituted arylene group, A group represented by the following structural formula (C) can be mentioned.
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • each Q 1 is independently a substituted or unsubstituted, linear or branched alkyl group having 1 to 9 carbon atoms; represents a substituted or unsubstituted aryl group having 15 or less carbon atoms, or a substituted or unsubstituted arylalkyl group having 15 or less carbon atoms, n is an integer from 0 to 8,
  • Q 2 is a single bond, a substituted or unsubstituted, linear or branched alkylene group, a substituted or unsubstituted arylene group, or an alkylene group (specifically, a substituted or unsubstituted, linear or branched alkylene a group in which the carbon adjacent to Y constituting the group) is substituted with a heteroatom, Si shown at the edge is connected to O adjacent to Z2 , and Q2 shown at the edge is connected to Y.
  • Q2 shown at the end is connected to Y means that Si adjacent to Q2 shown at the end is connected to Y when Q2 shown at the end is a single bond.
  • Q 2 shown at the end is an alkylene group, an arylene group, or a group in which the carbon adjacent to Y constituting the alkylene group is substituted with a hetero atom, an alkylene group, an arylene group, or an alkylene group It means that the group in which the carbon adjacent to Y constituting
  • linking group is omitted because it overlaps with the description of the linking group of general formula AA-D2. Therefore, the description of the linking group of general formula AA-D2 can also be treated as the description of the linking group of general formula AM-Q1.
  • linking group of general formula (Z2-1) should be given as the linking group linking the amino group belonging to general formula (Z2-2) and the O adjacent to Z 2 .
  • the linking groups can be independent of each other. That is, each linking group can be a unique structure.
  • Z 2 which is neither a structure represented by general formula (Z2-1) nor a structure represented by general formula (Z2-2), is H, that is, a hydrogen atom, or a structure represented by general formula (Z2-S) is. If Z2 is H, gelation of the polyamic acid solution may easily occur.
  • the structure represented by the general formula (Z2-S) is preferable because it can suppress gelation of the polyamic acid solution.
  • Q S1 in general formula (Z2-S) the explanation of Q S1 is omitted since it overlaps with the explanation of R 1 in general formula AA-D1. Therefore, the description of R 1 in general formula AA-D1 can also be treated as the description of Q S1 . Since there is a preferred embodiment specific to Q S1 , a description of the preferred embodiment is added.
  • QS1 is preferably a methyl group, an ethyl group, or a phenyl group from the viewpoint of raw material availability.
  • silsesquioxane derivative represented by general formula AM-Q1 is the same procedure as described for general formula AA-Q1, except that a compound having an amino group is used instead of a compound having an acid anhydride group. It can be manufactured by such a procedure. In addition, in the compound having an amino group, the amino group may be protected.
  • the novel silsesquioxane compound A is selected from the thiol group of condensate B, which is a thiol group-containing silsesquioxane compound, vinyl group, alkenyl group, cycloalkenyl group, alkynyl group, and acid chloride group. It is a silsesquioxane compound obtained by reacting with a reactive group of dicarboxylic anhydride C having at least one reactive group.
  • the condensate B is a thiol group-containing trialkoxysilane a1 represented by the general formula: R 1 Si(OR 2 ) 3 , (Wherein, R 1 represents an organic group in which at least one hydrogen of an aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 8 carbon atoms is substituted with a thiol group, R 2 independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.) It is a condensate B of trialkoxysilanes a2 having no thiol group.
  • silsesquioxane compound A can also be partially specified as two repeating units. That is, the novel silsesquioxane compound A preferably has structural units represented by the following general formulas (1) and (2).
  • Q 1 represents a C 1-8 aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group
  • Q 2 is a single bond, a C 1-8 hydrocarbon group , an organic group in which one or more carbon atoms of a hydrocarbon group having 1 to 8 carbon atoms are substituted with oxygen, or a carbonyl group
  • X is a carbon-carbon bond or 4 to 10 carbon atoms is an aliphatic ring, an aromatic ring, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur, and one or more of the hydrogens bonded to them is substituted with a hydrocarbon group Well, 1.0 ⁇ m ⁇ 2.0 and 1.4 ⁇ n ⁇ 1.6.
  • Q3 represents an aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 8 carbon atoms, and 1.4 ⁇ n ⁇ 1.6.
  • novel silsesquioxane compound A can be suitably produced, for example, by a production method including the following steps in order.
  • thiol group-containing trialkoxysilanes a1 represented by the general formula: R 1 Si(OR 2 ) 3 ;
  • R 1 represents an organic group in which at least one hydrogen of an aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 8 carbon atoms is substituted with a thiol group
  • R 2 independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
  • a second step of obtaining A third step of obtaining a condensate B having a thiol group by mixing and condensing a polar solvent containing a basic catalyst and the reaction mixture y, and the condensate B, a vinyl group, an alkenyl group, a cycloalkenyl group, A fourth step of reacting with a dicarboxylic anhydride C having at least one reactive group selected from an alkynyl group and an acid chloride group.
  • thiol group-containing silsesquioxane compound (condensate B) and at least one reactive group selected from a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an acid chloride group It can also be obtained by reacting with a dicarboxylic anhydride C having
  • Condensate B is a condensate of thiol group-containing trialkoxysilanes a1 and trialkoxysilanes a2 having no thiol group.
  • Condensate B for example, an organic/inorganic hybrid resin Compoceran SQ (product name: SQ107 or SQ109, Arakawa Chemical Industries, Ltd.) can be used.
  • the condensate B synthesized by a method including the above 1st to 3rd steps can be used.
  • thiol group-containing trialkoxysilanes a1 represented by the general formula: R 1 Si(OR 2 ) 3 , trialkoxysilanes a2 having no thiol group, and water are combined with an acidic catalyst. It is a step of obtaining a reaction mixture x by hydrolyzing with
  • R 1 represents an organic group in which at least one hydrogen of an aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 8 carbon atoms is substituted with a thiol group
  • R 2 independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
  • “1 to 8 carbon atoms” are intended to modify aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, but from the relationship with the minimum carbon number, more accurately means an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • R 1 is a hydrocarbon group having 1 to 8 carbon atoms having a straight chain, a branched chain, or an aliphatic ring, or a carbon represents an organic group in which at least one hydrogen of an aromatic hydrocarbon group of numbers 6 to 8 is substituted with a thiol group;
  • R 1 is preferably a linear hydrocarbon group from the viewpoint of imparting flexibility to the polymer chain, and preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of enhancing heat resistance.
  • R 2 independently of each other may have a hydrogen atom, a linear or branched chain, or an aliphatic ring-containing hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group; Represents 6-8 aromatic hydrocarbon groups.
  • R 2 is preferably an alkyl group having 1 to 4 carbon atoms. A methyl group or an ethyl group is particularly preferred.
  • component (a1)) Specific examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercapto propyltributoxysilane, 1,4-dimercapto-2-(trimethoxysilyl)butane, 1,4-dimercapto-2-(triethoxysilyl)butane, 1,4-dimercapto-2-(tripropoxysilyl)butane, 1,4-dimercapto-2-(tributoxysilyl)butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyl tripropoxysilane, 2-mercaptomethyl-3-mercapto
  • Examples of trialkoxysilanes a2 having no thiol group include compounds represented by the general formula: R 3 Si(OR 2 ) 3 .
  • R 3 represents an aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 8 carbon atoms
  • R 2 each independently represents a hydrogen atom, a 1 to 8 aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group.
  • R 3 is a hydrocarbon group having 1 to 8 carbon atoms having a linear or branched chain or an aliphatic ring, or a hydrocarbon group having 6 to 8 carbon atoms which may have a hydrocarbon group. represents an aromatic hydrocarbon group.
  • R 2 is as described for component (a1), and may be the same as or different from R 2 in component (a1).
  • component (a2) examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • Component (a2) can be used either singly or in combination of two or more. By using these, the amount of thiol groups can be adjusted, so that the degree of cross-linking of the finally obtained polyimide can be adjusted and the proportion of the inorganic component in the polyimide can be increased.
  • the molar ratio of the trialkoxysilanes a2 in the alkoxysilanes is preferably 0.1 or more and 0.7 or less. It is more preferably 2 or more and 0.7 or less.
  • the larger the molar ratio the smaller the amount of thiol groups contained per molecule, and the smaller the molar ratio, the larger the amount of thiol groups.
  • the resulting polyimide chain is appropriately crosslinked, and the effect of improving physical properties is sufficient.
  • Condensate B which is a thiol group-containing silsesquioxane, can be obtained by using component (a1) and component (a2), hydrolyzing them, and then condensing them.
  • the alkoxy groups contained in the component (a1) and the component (a2) are converted into silanol groups by the hydrolysis reaction, and alcohol is produced as a by-product.
  • the amount of water required for the hydrolysis reaction is expressed as a molar ratio ([number of moles of water used for hydrolysis reaction]/[total number of moles of each alkoxy group contained in component (a1) and component (a2)]).
  • 0.4 to 10 are preferred. When this molar ratio is 0.4 or more and less than 0.5, some alkoxy groups will remain in the resulting thiol group-containing silsesquioxane, but adhesion to inorganic materials can be improved. Moreover, in the case of 0.5 to 10, substantially no alkoxy group remains in the thiol group-containing silsesquioxane to be obtained, and a thick film cured product can be easily produced.
  • dialkoxysilanes and/or tetraalkoxysilanes may be further used within a range that does not impair the effects of the present invention (for example, 50 mol % or less). It is possible.
  • any conventionally known acidic catalyst that can function as a hydrolysis catalyst can be used. However, since it is necessary to substantially remove the acid catalyst after the hydrolysis reaction, it is preferably one that can be easily removed. These include formic acid, which has a low boiling point and can be removed by vacuum, and solid acid catalysts, which can be easily removed by methods such as filtration.
  • solid acid catalysts examples include cation exchange resins, activated clay, and carbon-based solid acids.
  • cation exchange resins are preferable because they have high catalytic activity and are easily available.
  • As the cation exchange resin a strong acid type cation exchange resin and a weak acid type cation exchange resin can be used.
  • Diaion SK series, Diaion UBK series, Diaion PK series, Diaion HPK25/PCP series all product names of Mitsubishi Chemical Corporation
  • the type of ion-exchange resin to be used can be arbitrarily selected depending on the reaction rate, suppression of side reactions, etc., strongly acidic ion-exchange resins are particularly preferred from the viewpoint of reactivity.
  • the amount of the acid catalyst to be added is preferably 0.1 to 25 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass in total of the components (a1) and (a2).
  • it is 25 parts by mass or less, it tends to be easy to remove in a later step, which tends to be economically advantageous.
  • the amount is 0.1 parts by mass or more, the reaction can proceed appropriately, and there is a tendency that the reaction time does not become too long.
  • the reaction temperature and time can be arbitrarily set according to the reactivity of component (a1) and component (a2), but are usually about 0 to 100°C, preferably about 20 to 60°C for about 1 minute to 2 hours.
  • the hydrolysis reaction can be carried out in the presence or absence of a solvent, preferably without solvent.
  • a solvent the type of solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as used in the condensation reaction described below.
  • the second step is to remove the acidic catalyst from the reaction mixture x to obtain a reaction mixture y. That is, it is necessary to substantially remove the acid catalyst from the system after the hydrolysis reaction in the first step is completed. If not removed, the reaction does not proceed in the condensation reaction described later, the silanol group is not completely consumed, or the system gels due to an abnormal increase in the molecular weight. Oxane (condensate B) cannot be obtained.
  • the method for removing the acidic catalyst can be appropriately selected from various known methods depending on the catalyst used. For example, as described above, when formic acid is used, it can be easily removed by reducing pressure, and when a solid acid catalyst is used, it can be easily removed by a method such as filtration after completion of the condensation reaction.
  • by-product alcohol and excess water may be removed by a method such as decompression. Further, by diluting with the solvent used for the condensation reaction after removal, it is possible to facilitate the addition of the hydrolyzate in the subsequent condensation reaction.
  • the third step is a step of obtaining a condensate B having a thiol group by mixing and condensing a polar solvent containing a basic catalyst and the reaction mixture y.
  • a condensation reaction water is by-produced between the silanol groups, and alcohol is by-produced between the silanol groups and the alkoxy groups, forming siloxane bonds.
  • a conventionally known basic catalyst capable of functioning as a dehydration condensation catalyst can be arbitrarily used in the condensation reaction.
  • the basic catalyst preferably has a high basicity, and specific examples thereof include alkali salts such as sodium hydroxide (NaOH), potassium hydroxide (KOH) and calcium hydroxide (Ca(OH) 2 ); Organic amines such as 8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and ammonium hydroxides such as Any one of the exemplified compounds can be used alone or in combination as appropriate. Among the exemplified compounds, tetramethylammonium hydroxide is particularly preferred because of its high catalytic activity and easy availability. In addition, when these basic catalysts are used as an aqueous solution, the hydrolysis reaction proceeds even in the condensation reaction step. , should be adjusted accordingly.
  • alkali salts such as sodium hydroxide (NaOH), potassium hydroxide (KOH)
  • the amount of the basic catalyst to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass in total of component (a1) and component (a2). more preferred. If the amount of the basic catalyst added is 5 parts by mass or less, the cured product prepared using the obtained thiol group-containing silsesquioxane (condensate B) is difficult to color, and when removing the catalyst, it is removed. This tends to make the process of On the other hand, when the amount is 0.01 part by mass or more, the reaction can proceed appropriately, and there is a tendency that the reaction time does not become too long.
  • the reaction temperature can be arbitrarily set according to the reactivity of component (a1) and component (a2), but is usually about 40 to 150°C, preferably about 60 to 100°C.
  • the condensation reaction is preferably carried out in the presence of a polar solvent, and from the viewpoint of the stability of the obtained silsesquioxane compound A and its copolymer amic acid solution and the quality of the resulting film, a solvent such as toluene is used. It is more preferable not to contain a non-polar solvent.
  • polar solvent a polar solvent that exhibits compatibility with water is preferable, and glycol ethers are particularly preferable.
  • glycol ethers dialkyl glycol ether solvents are particularly preferred.
  • dialkyl glycol ether-based solvents compatible with water include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.
  • Glycol ether acetate solvents such as propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can also be used.
  • the condensation reaction can also be carried out by setting the reaction temperature to a polar solvent containing a dehydration condensation catalyst and sequentially adding a solution containing the hydrolyzate obtained in the hydrolysis reaction.
  • the method of addition can be appropriately selected from various known methods.
  • the time required for addition can be arbitrarily set depending on the reactivity of component (a1) and component (a2), but is usually about 30 minutes to 12 hours.
  • the total molar ratio of unreacted alkoxy groups ([total number of moles of unreacted alkoxy groups]/[total number of moles of each alkoxy group contained in component (a1) and component (a2)]) is 0.5. It is preferable to proceed so that it becomes 2 or less, and it is more preferable to make it substantially 0. When this molar ratio is more than 0 and 0.2 or less, some alkoxy groups will remain in the resulting thiol group-containing silsesquioxane (condensate B), but adhesion to inorganic materials is preferable in terms of improvement.
  • the condensation reaction is preferably carried out by diluting with a solvent so that the total concentration of component (a1) and component (a2) is about 2 to 80% by mass, more preferably 15 to 75% by mass. It is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction, because these can be distilled off from the reaction system. A concentration of 2% by mass or more is preferable because the thiol group-containing silsesquioxane (condensate B) contained in the obtained curable composition is sufficient. When it is 80% by mass or less, it becomes difficult to gel during the reaction, and the resulting condensate B tends to have an appropriate molecular weight.
  • the removal method can be appropriately selected from various known methods according to the catalyst used. For example, when tetramethylammonium hydroxide is used, it can be removed by adsorption and removal with a cation exchange resin after completion of the condensation reaction.
  • ⁇ Fourth step> the condensate B and a dicarboxylic anhydride C having at least one reactive group selected from a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an acid chloride group. This is the step of reacting.
  • a dicarboxylic anhydride having a functional group capable of reacting with a thiol group is used as the dicarboxylic anhydride C (hereinafter referred to as component (C)).
  • component (C) dicarboxylic anhydrides having vinyl groups, acryl groups, methacryl groups, allyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, or acid chloride groups
  • a dicarboxylic anhydride having a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or an acid chloride group can be used.
  • the dicarboxylic anhydride C preferably has the following structure.
  • the following compounds and compounds having an acid chloride group are particularly preferred due to their high reactivity.
  • dicarboxylic anhydride C which has low reactivity, it is difficult to proceed the reaction completely with only UV light, so it is preferable to use an oxidation catalyst such as oxygen or iron chloride together.
  • phthalic anhydride compounds having an aromatic ring structure are desirable from the viewpoint of improving the heat resistance of the resulting polyimide and suppressing yellowing under high-temperature conditions.
  • Maleic anhydride and cyclohexanedicarboxylic anhydride having a cyclic structure are desirable in terms of enhancing colorless transparency.
  • thiol group-containing silsesquioxane (condensate B) and the dicarboxylic anhydride C
  • a thiol-ene reaction or a reaction between a thiol group and an acid chloride group can be used.
  • the reaction mechanism differs depending on the type of carbon-carbon double bond and the presence or absence of a radical polymerization initiator. That is, when a compound having a vinyl group or an allyl group with low radical polymerizability is used as component (C), only the en-thiol reaction proceeds, and the thiol group in condensate B and component (C) Carbon-carbon double bonds react at approximately 1:1 (molar ratio) and are preferred. On the other hand, when a compound having a highly radically polymerizable acrylic group or methacrylic group is used as the component (C), the carbon-carbon double bond in the component (C) is particularly affected when a radical polymerization initiator is used in combination.
  • the polymerization reaction also proceeds in parallel, and the thiol group in the condensate B and the carbon-carbon double bond in the component (C) react at a ratio of about 1: 1 to 100 (molar ratio), so the effect of the invention is You may not get enough.
  • the molar ratio [number of moles of thiol groups contained in condensate B]/[component (C) The number of moles of carbon-carbon double bonds contained in]) is preferably 0.9 to 2.5, more preferably 1.0.
  • an ultraviolet light source As a thiol-ene reaction initiator, an ultraviolet light source, an organic material, an inorganic material, or oxygen can be used.
  • an ultraviolet light source for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, or an ultraviolet LED can be used.
  • Usable initiators are not particularly limited, and conventionally known photo cationic initiators, photo radical initiators, oxidizing agents, etc. can be arbitrarily selected.
  • photocationic initiators include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate, etc., which are compounds that generate acid upon irradiation with ultraviolet rays. -6974, UVI-6990 (all trade names of Union Carbide Co., USA), Irgacure 264 (manufactured by BASF), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), and the like.
  • the amount of the cationic photopolymerization initiator to be used is usually about 10 parts by weight or less, preferably 1 to 5 parts by weight, per 100 parts by weight of the composition.
  • the photoradical initiator examples include Darocure 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all trade names manufactured by BASF), benzophenone, and the like, preferably about 5 parts by weight or less per 100 parts by weight of the composition. is 0.1 to 2 parts by mass.
  • the reaction can be accelerated by adding an oxidizing agent such as iron oxide or iron chloride.
  • an ultraviolet light source or oxygen for the reaction without using a photoreaction initiator or photosensitizer.
  • condensation B silanol group amount of the silsesquioxane
  • unreacted acid chloride groups may be copolymerized with polyamic acid to form polyamidoimide.
  • organic bases are N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidinone, imidazole, N-methylcaprolactam, imidazole, N,N-dimethylaniline and N,N-diethylaniline.
  • tertiary amines include pyridine, collidine, lutidine and triethylamine.
  • inorganic bases include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
  • a volatile base for substrate film applications that require high heat resistance and transparency, it is desirable to use a volatile base for the reaction. By removing hydrochloric acid by adding a base or heating the solution, gelation due to excessive reaction of silsesquioxane can be suppressed.
  • solvents used for the reaction Benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N- Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, hexamethylsulfolamide, cresol, pheno xylenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme, propylene glycol monomethyl ether acetate (
  • N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone as the main component of the organic solvent.
  • a poor solvent such as toluene or xylene may be used to the extent that the polyimide resin or its precursor does not precipitate.
  • the silsesquioxane compound A having an acid anhydride group obtained in the fourth step can be used as it is after the reaction. It can also be used as a powder.
  • silsesquioxane compound A Having an Acid Anhydride Group
  • the silsesquioxane compound A that can be obtained as described above preferably has structural units represented by the following general formulas (1) and (2). It is more preferred to have only the structural units represented.
  • Q 1 represents a C 1-8 aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group
  • Q 2 is a single bond, a C 1-8 hydrocarbon group , an organic group in which one or more carbon atoms of a hydrocarbon group having 1 to 8 carbon atoms are substituted with oxygen, or a carbonyl group
  • X is a carbon-carbon bond or 4 to 10 carbon atoms is an aliphatic ring, an aromatic ring, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur, and one or more of the hydrogens bonded to them is substituted with a hydrocarbon group Well, 1.0 ⁇ m ⁇ 2.0 and 1.4 ⁇ n ⁇ 1.6.
  • Q3 represents an aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 8 carbon atoms, and 1.4 ⁇ n ⁇ 1.6.
  • Q 1 in general formula (1) may have a hydrocarbon group having 1
  • Q 1 examples include a hydrocarbon group in which the Si atom and the S atom of the compound exemplified as the thiol group-containing trialkoxysilanes a1 are bonded, or an aromatic hydrocarbon group.
  • Q 2 is a hydrocarbon group having 1 to 8 carbon atoms having a single bond, a straight chain, or a branched chain, an oxygen-containing hydrocarbon group in which one or more of the carbon atoms is substituted with oxygen, or a carbonyl group .
  • Q2 is preferably a straight-chain hydrocarbon group from the viewpoint of imparting flexibility to the polymer chain, and is preferably a single bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group from the viewpoint of improving heat resistance.
  • X is a carbon-carbon bond, or an aliphatic ring having 4 to 10 carbon atoms, an aromatic ring having 6 to 10 carbon atoms, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur It is a ring, and one or more of the hydrogen atoms attached thereto may be substituted with a hydrocarbon group.
  • X is preferably a carbon-carbon bond from the viewpoint of imparting flexibility to the polymer chain, and preferably a single bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group from the viewpoint of improving heat resistance.
  • X is an aromatic hydrocarbon group, it is preferable from the viewpoint of being able to improve heat resistance and suppress discoloration under high temperature conditions.
  • Q2 and X include reactive residues of compounds exemplified as dicarboxylic anhydride C, excluding dicarboxylic anhydride groups.
  • the following chemical formulas show examples in which X is a heterocyclic ring in which a part of carbon atoms constituting an aliphatic or aromatic ring is substituted with oxygen or sulfur.
  • n is 1.0 ⁇ m ⁇ 2.0, and m is preferably 1 from the viewpoint of small steric hindrance and high reactivity of the dicarboxylic anhydride group.
  • m is 1.0 ⁇ m ⁇ 2.0 (that is, other than an integer)
  • a component (a1) having one thiol group and a component having two thiol groups are used in combination.
  • n is 1.4 ⁇ n ⁇ 1.6, and from the viewpoint of forming a more uniform three-dimensional structure, n is preferably 1.5.
  • the reason why n is assumed to be other than 1.5 is to allow a small amount of not only trialkoxysilane but also dialkoxysilane and tetraalkoxysilane to be mixed in the raw material.
  • Q 3 in the general formula (2) may have a hydrocarbon group with 1 to 8 carbon atoms having a straight chain, a branched chain, or an aliphatic ring, or a hydrocarbon group with 6 carbon atoms. represents an aromatic hydrocarbon group of ⁇ 8.
  • Q3 is preferably a short-chain or branched-chain hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of suppressing crystallization and improving heat resistance.
  • Specific examples of Q3 include a hydrocarbon group or an aromatic hydrocarbon group that bonds to the Si atom of the compounds exemplified as the trialkoxysilanes a2.
  • the molar ratio of the structural units represented by the general formula (2) is preferably 0.1 or more and 0.7 or less, more preferably 0.2 or more and 0.7 or less.
  • the resulting polyimide chain is appropriately crosslinked, and the effect of improving physical properties is sufficient.
  • the number of acid anhydride groups (number of functional groups) per molecule of the silsesquioxane compound A is preferably 2-10, more preferably 2.5-6. When the number of functional groups is within this range, the resulting polyimide chain is moderately crosslinked, so that the effect of improving physical properties is sufficient.
  • the molecular weight of the silsesquioxane compound A is preferably 400-5000, more preferably 600-3000. When the molecular weight is within this range, the resulting polyimide is less likely to become non-uniform, and a uniform crosslinked structure is likely to be obtained.
  • a method for obtaining the silsesquioxane compound A having such a structure at the stage of the condensate B (thiol group-containing silsesquioxane compound), a cage-shaped, partially open cage-shaped, or ladder-shaped silsesquioxane A method of obtaining an oxane compound in advance and a method of using a commercially available thiol group-containing silsesquioxane compound having such a structure are exemplified.
  • Condensate B can be synthesized by dehydration condensation of dialkylsilanediol or dehydrochlorination reaction of dialkylsilanediol and dialkyldichlorosilane.
  • the catalyst, solvent, and substrate concentration used By adjusting the catalyst, solvent, and substrate concentration used, the production ratio of the specific structure can be increased.
  • a specific structure can be isolated by purifying the obtained product by methods such as recrystallization, solvent washing, and column separation. The method is not particularly limited.
  • T H 8 which is a type of cage structure, can be synthesized, for example, by hydrolyzing trichlorosilane in the presence of iron chloride (Bull. Chem. Soc. Jpn., 73, 215 (2000)).
  • T H 8 Various derivatives can be synthesized by further chemically modifying T H 8 as a starting material.
  • the organic group is introduced by reacting an alkenyl compound in the presence of a platinum catalyst.
  • Reaction of T H 8 with chlorine gives T Cl 8 and further reaction with methyl orthoformate can introduce a methoxy group.
  • T Ph 4 T Ph 3 (ONa) 3 having a double-decker structure is produced almost quantitatively when trimethoxy(phenyl)silane is hydrolyzed in the presence of sodium hydroxide.
  • the polyamic acid of the present invention is at least a copolymer reaction product of a silsesquioxane derivative (that is, a silsesquioxane compound), carboxylic acids, and diamines as described above.
  • a silsesquioxane derivative that is, a silsesquioxane compound
  • carboxylic acids that is, a silsesquioxane compound
  • diamines as described above.
  • polyimides in general, there is a trade-off relationship between practical properties such as heat resistance and mechanical properties, and colorlessness (transparency or whiteness). In particular, toughness is improved while maintaining other main properties. It would be desirable to have a method for producing a polyimide film having a high density.
  • a polyimide film can be obtained, for example, by including a step of synthesizing polyamic acid in a solution, a step of forming a film from the polyamic acid solution, and a step of imidizing the polyamic acid.
  • Polyamic acid can be synthesized, for example, by reacting at least carboxylic acids, diamines and a silsesquioxane compound in a solvent. That is, at least carboxylic acids and diamines can be used as monomer components other than the silsesquioxane compound.
  • the carboxylic acids are not particularly limited, and include alicyclic tetracarboxylic anhydrides and aromatic tetracarboxylic anhydrides, tricarboxylic acids, and dicarboxylic acids that are commonly used in polyimide synthesis, polyamideimide synthesis, and polyamide synthesis. can be used.
  • Aromatics are preferred from the viewpoint of heat resistance, and alicyclics are preferred from the viewpoint of transparency. These may be used alone or in combination of two or more.
  • the alicyclic tetracarboxylic anhydrides used in the present invention include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and 1,2,3,4-cyclohexane.
  • Tetracarboxylic acid 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3′,4,4′-bicyclohexyltetracarboxylic acid, bicyclo[2,2,1]heptane-2,3,5,6 -tetracarboxylic acid, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic acids, tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4:5,8:9,10-trimethanoanthracene-2,3,6,7-tetracarboxylic acid, Decahydronaphthalene-2,3,6,7-tetracarboxylic acid, Decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracar
  • dianhydrides having two acid anhydride structures are preferred, particularly 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic An acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is even more preferred. In addition, these may be used independently and may use 2 or more types together.
  • aromatic tetracarboxylic anhydrides used in the present invention include 4,4′-(2,2-hexafluoroisopropylidene)diphthalic acid, 4,4′-oxydiphthalic acid, bis(1,3-dioxo-1,3 -dihydro-2-benzofuran-5-carboxylic acid) 1,4-phenylene, bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl)benzene-1,4-dicarboxylate, 4,4′-[4,4′-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(benzene-1,4-diyloxy)]dibenzene-1,2-dicarbon acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 4,4′-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-
  • Tricarboxylic acids include aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, diphenylether-3,3′,4′-tricarboxylic acid, and diphenylsulfone-3,3′,4′-tricarboxylic acid.
  • acids or hydrogenated products of the above aromatic tricarboxylic acids such as hexahydrotrimellitic acid; Glycol bistrimellitate, and their monoanhydrides and esters.
  • monoanhydrides having one acid anhydride structure are preferred, and trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferred. In addition, these may be used individually and may be used in combination.
  • Dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid, or the above aromatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids and hydrogenated products thereof are preferred, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, and 4,4'-oxydibenzenecarboxylic acid are particularly preferred.
  • dicarboxylic acids may be used alone or in combination.
  • the carboxylic acids are preferably one or more compounds represented by chemical formulas selected from the following.
  • the polyamic acid has a structural unit derived from one or more of these compounds.
  • the polyamic acid may not have structural units derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, that is, BPDA.
  • aromatic diamines examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 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]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,
  • Alicyclic diamines include, for example, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propyl cyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 9,10-bis(4-aminophenyl)adenine, 2,4-bis(4- aminophenyl)cyclobut
  • Diamines preferably include 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) or 4,4'-diaminobenzanilide (DABA), and 4,4'- Diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) or 4,4'-diaminobenzanilide (DABA) are more preferred.
  • TFMB 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl
  • DABA 4,4'-diaminobenzanilide
  • the number of moles of structural units derived from the silsesquioxane derivative (provided that the silsesquioxane derivative If it has more than one anhydride group, this number of moles is the total number of moles of the silsesquioxane derivative divided by the total number of anhydride groups of the silsesquioxane derivative and doubled) is 0.0001 times or more the sum of the number of moles of the structural unit derived from the silsesquioxane derivative and the number of moles of the structural unit derived from the carboxylic acid.
  • the total number of acid anhydride groups in the silsesquioxane derivative means the number of acid anhydride groups per molecule of the silsesquioxane derivative. That is, the molar content of structural units derived from a silsesquioxane derivative (specifically, the molar content based on a divalent monomer, that is, the molar content in terms of divalent) is 0.0001. mol% or more. The molar content is a value obtained by the following calculation.
  • nA is the number obtained by dividing the total number of moles of structural units derived from a silsesquioxane derivative by the total number of acid anhydride groups and multiplying it by two
  • nD is the number of moles of structural units derived from carboxylic acids. number.
  • total number of acid anhydride groups means the number of acid anhydride groups per molecule of the silsesquioxane derivative.
  • the toughness of the polyimide film can be effectively improved.
  • the number of moles of structural units derived from the silsesquioxane derivative is preferably 0.001 times or more, more preferably 0.005 times or more, and still more preferably 0.01 times or more.
  • the number of moles of structural units derived from the silsesquioxane derivative is 0.09 times or less. That is, the molar content of structural units derived from the silsesquioxane derivative is 0.09 mol % or less.
  • the degree of increase in CTE derived from the silsesquioxane derivative can be suppressed. That is, CTE can be maintained. That is, a significant increase in CTE can be suppressed.
  • the thermal decomposition temperature and glass transition temperature can be maintained. That is, it is possible to suppress a large decrease in thermal decomposition temperature and glass transition temperature. Moreover, the toughness of the polyimide film can be effectively improved.
  • silsesquioxane derivative has SiOH groups (e.g., residual SiOH groups)
  • gelation of the polyamic acid solution tends to occur (this tendency is particularly pronounced for random type structures).
  • gelation of the polyamic acid solution can be suppressed or reduced by setting the number of moles of structural units derived from the silsesquioxane derivative to 0.09 times or less. That is, the temporal stability of the polyamic acid solution can be improved.
  • the number of moles of structural units derived from the silsesquioxane derivative is preferably 0.08 times or less.
  • the number of moles of structural units derived from the silsesquioxane derivative may be 0.07 times or less, or may be 0.06 times or less.
  • the number of moles of structural units derived from the silsesquioxane derivative (provided that the silsesquioxane derivative has two This number of moles is the total number of moles of the silsesquioxane derivative divided by the total number of amino groups of the silsesquioxane derivative and doubled) is the silsesquioxane It is at least 0.0001 times the sum of the number of moles of the structural units derived from the derivative and the number of moles of the structural units derived from the diamines.
  • the total number of amino groups in the silsesquioxane derivative means the number of amino groups per molecule of the silsesquioxane derivative. That is, the molar content of structural units derived from a silsesquioxane derivative (specifically, the molar content based on a divalent monomer, that is, the molar content in terms of divalent) is 0.0001. mol% or more. The molar content is a value obtained by the following calculation.
  • nA is the total number of moles of structural units derived from silsesquioxane derivatives divided by the total number of amino groups and doubled
  • nD is the number of moles of structural units derived from diamines. be.
  • total number of amino groups means the number of amino groups per molecule of the silsesquioxane derivative.
  • the toughness of the polyimide film can be effectively improved.
  • the number of moles of structural units derived from the silsesquioxane derivative is preferably 0.001 times or more, more preferably 0.005 times or more, and still more preferably 0.01 times or more.
  • the number of moles of structural units derived from the silsesquioxane derivative is 0.09 times or less. That is, the molar content of structural units derived from the silsesquioxane derivative is 0.09 mol % or less.
  • the degree of increase in CTE derived from the silsesquioxane derivative can be suppressed. That is, CTE can be maintained. That is, a significant increase in CTE can be suppressed.
  • the thermal decomposition temperature and glass transition temperature can be maintained. That is, it is possible to suppress a large decrease in thermal decomposition temperature and glass transition temperature. Moreover, the toughness of the polyimide film can be effectively improved.
  • silsesquioxane derivative has SiOH groups (e.g., residual SiOH groups)
  • gelation of the polyamic acid solution tends to occur (this tendency is particularly pronounced for random type structures).
  • gelation of the polyamic acid solution can be suppressed or reduced by setting the number of moles of structural units derived from the silsesquioxane derivative to 0.09 times or less. That is, the temporal stability of the polyamic acid solution can be improved.
  • the number of moles of structural units derived from the silsesquioxane derivative is preferably 0.08 times or less.
  • the number of moles of structural units derived from the silsesquioxane derivative may be 0.07 times or less, or may be 0.06 times or less.
  • any solvent can be used as long as it dissolves the polyamic acid and its monomers. be done.
  • the aprotic solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethyl amide solvents such as urea; lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoricamide and hexamethylphosphine triamide; Examples include sulfur-containing solvents; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
  • Phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and the like.
  • Ether and glycol solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether , tetrahydrofuran, 1,4-dioxane, and the like.
  • the solvent preferably contains N-methyl-2-pyrrolidone, N,N'-dimethylacetamide, or ⁇ -butyrolactone as a main component.
  • the above solvents may be used alone or in combination of two or more.
  • the reaction temperature is preferably -30 to 200°C, more preferably 20 to 180°C, and particularly preferably 20 to 100°C. Stirring is continued at room temperature (20 to 25° C.) or at an appropriate reaction temperature, and the reaction can be terminated when the viscosity of the polyimide precursor becomes constant.
  • the above reaction can usually be completed in 3 to 100 hours.
  • the polyamic acid composition of the present invention contains the above polyamic acid and a solvent.
  • the polyamic acid composition may contain a solvent different from the solvent used during synthesis, it is preferable to contain the solvent used during synthesis from the viewpoint of avoiding the complexity of the manufacturing process. Therefore, the main component of the solvent contained in the polyamic acid composition is preferably N-methyl-2-pyrrolidone, N,N'-dimethylacetamide, or ⁇ -butyrolactone.
  • the content of the polyamic acid is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, in the polyamic acid composition from the viewpoint of film thickness during film formation. When the content is within this range, a thin film having a thickness that is excellent in handling can be obtained.
  • the polyamic acid composition may further contain optional components such as adhesion promoters, surfactants, leveling agents, antioxidants, UV absorbers, chemical imidizing agents, colorants, and bluing agents.
  • it may further contain a filler or the like that can be contained in the polyimide film.
  • the polyimide of the present invention is obtained by imidating the polyamic acid described above.
  • Polyimide can be obtained, for example, by heating the polyamic acid. By heating, the carboxyl groups of the polyamic acid undergo dehydration ring closure, and the polyamic acid is imidized to form a polyimide structure.
  • Polyimide can be obtained by heating polyamic acid in a solvent.
  • the heating temperature for imidizing the polyamic acid is preferably 150 to 220° C. in the solvent.
  • polyimide can be provided as a film-like or film-like molded product by applying a polyamic acid composition containing a solvent to a substrate and heating it.
  • the heating temperature for imidizing the polyamic acid is preferably 250 to 400° C. when the solvent is at least a certain amount and in a dry state.
  • Coloring due to oxidation of terminal amino groups can be suppressed by adding a terminal amino group blocking agent to a polyamic acid composition containing a solvent and heat-treating.
  • the terminal amino group-capping agent is not particularly limited as long as it is a compound that reacts with an amino group to form a chemical bond.
  • acetic anhydride can be used.
  • a tertiary amine is more preferable as the tertiary amine.
  • heterocyclic tertiary amines include pyridine, 2,5-diethylpyridine, picoline, quinoline and isoquinoline.
  • the polyimide film of the present invention contains the above polyimides.
  • the polyimide film is composed of two or more layers, at least one layer may contain the polyimide of the present invention.
  • a polyimide film can be obtained, for example, by casting a polyamic acid solution on a substrate, heating it to volatilize the solvent, and forming a uniform green film with a thickness of 1 to 100 ⁇ m, which is then imidized.
  • Substrates used for forming a film by such a casting method include polymer films, glass plates, silicon rubber plates, metal plates, and the like.
  • polyethylene terephthalate film A4100 manufactured by Toyobo Co., Ltd.
  • a method of adjusting the concentration of the polyamic acid solution, a method of adjusting the gap between the coaters, and a method of repeatedly casting to obtain the desired film thickness are adopted.
  • a substrate having a desired film thickness can be produced.
  • the obtained green film is thermally imidized to obtain a polyimide film.
  • the polyimide film may have a single layer structure, or may have a laminated structure of two or more layers. From the viewpoint of the physical strength of the polyimide film and the ease of peeling from the inorganic substrate, it preferably has a lamination structure of two or more layers, and may have a lamination structure of three or more layers.
  • the physical properties (yellowness index, total light transmittance, haze, etc.) in the case where the polyimide film has a laminate structure of two or more layers refer to the values of the entire polyimide film unless otherwise specified.
  • the thickness of the polyimide film is preferably 3 ⁇ m or more and 75 ⁇ m or less.
  • the film thickness is preferably 6 ⁇ m or more, more preferably 12 ⁇ m or more.
  • the upper limit is preferably 60 ⁇ m, more preferably 45 ⁇ m or less.
  • the thickness of the film is related to the bendability, and within a predetermined range, the film can be bent relatively easily.
  • the total light transmittance of the polyimide film in the present invention is preferably 75% or more, more preferably 85% or more, even more preferably 87% or more, and still more preferably 88% or more.
  • the upper limit of the total light transmittance of the polyimide film is not particularly limited, it is preferably 98% or less, more preferably 97% or less for use as a flexible electronic device.
  • the haze of the polyimide film in the present invention is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.5 or less, and still more preferably 0.3 or less.
  • the yellowness index of the polyimide film in the present invention (hereinafter also referred to as "yellow index" or “YI”) is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 5 or less.
  • the lower limit of the yellowness index of the polyimide film is not particularly limited, but in order to use it as a flexible electronic device, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. is.
  • the thickness direction retardation (Rth) of the polyimide film in the present invention is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and still more preferably 100 nm or less.
  • the lower limit of Rth of the polyimide film is not particularly limited, it is preferably 0.1 nm or more, more preferably 0.5 nm or more for use as a flexible electronic device.
  • the polyimide film of the present invention can also be realized by stretching in the process of forming the polyimide film.
  • a polyimide solution is applied to a polyimide film-producing support, dried to form a polyimide film containing a solvent of 1 to 50% by mass, and further on a polyimide film-producing support or peeled off from the support. 1.5 to 4.0 times in the MD direction and 1.4 to 3.0 times in the TD direction in the process of drying the polyimide film containing 1 to 50% by mass of solvent at a high temperature.
  • thermoplastic polymer film is used as a support for producing a polyimide film, and after stretching the thermoplastic polymer film and the polyimide film at the same time, the stretched polyimide film is peeled off from the thermoplastic polymer film.
  • the average coefficient of linear expansion (CTE) of the polyimide film between 50°C and 200°C is preferably 35 ppm/K or less, more preferably 18 ppm/K or less, and even more preferably 9 ppm/K or less.
  • the lower limit of the coefficient of linear expansion is -5 ppm/K, preferably -2 ppm/K.
  • the difference in linear expansion coefficient between the polymer film and the substrate is 10 ppm/K or less.
  • the polyimide film may contain a filler.
  • the filler is not particularly limited, and includes silica, carbon, ceramics, etc. Among them, silica is preferable. These fillers may be used alone or in combination of two or more. Addition of the filler imparts projections to the surface of the polyimide film, thereby increasing the slipperiness of the polyimide film surface. Also, by adding a filler, the CTE and Rth of the polyimide film can be kept low.
  • the average particle size of the filler is preferably 1 nm or more, more preferably 5 nm or more. Also, it is preferably 1 ⁇ m or less, more preferably 500 nm or less, and still more preferably 100 nm or less.
  • the content of the filler in the polyimide film is preferably adjusted according to the average particle size of the filler.
  • the particle size of the filler is 30 nm or more, it is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, still more preferably 0.01 to 2% by mass, and particularly It is preferably 0.01 to 1% by mass.
  • the average particle diameter is less than 30 nm, it is preferably 0.01 to 50% by mass, more preferably 0.01 to 40% by mass, still more preferably 0.01 to 30% by mass, Particularly preferably, it is 0.01 to 20% by mass.
  • the method of adding a filler in a polyimide film is not particularly limited, but when preparing the above-mentioned polyamic acid (polyimide precursor) solution, or after preparation, a method of adding powder, a form of filler / solvent (slurry ), and the method of adding in the form of a slurry is particularly preferred.
  • the slurry is not particularly limited, but a slurry in which silica having an average particle size of 10 nm is dispersed in N,N-dimethylacetamide (DMAC) at a concentration of 20% by mass (for example, "Snowtex (registered trademark) DMAC manufactured by Nissan Chemical Industries, Ltd.
  • DMAC N,N-dimethylacetamide
  • the polyimide film may contain a coloring agent.
  • the YI of the film can be reduced.
  • the coloring agent include organic pigments, inorganic pigments, and dyes. Organic pigments and inorganic pigments are preferred in order to improve the heat resistance, reliability, and light resistance of the colored film.
  • the colorant preferably has a 1% heat weight loss temperature of 220° C. or higher.
  • the 1% heat weight loss temperature of the colorant can be measured using a TGA apparatus (TGA-50, Shimadzu Corporation). About 10 mg of the colorant is placed on an aluminum pan, and the measurement is performed in a nitrogen atmosphere at a heating rate of 10° C./min. Then, the temperature at which the weight is reduced by 1% (1% weight reduction temperature: Td 1 ) can be read using the weight at the time of reaching 150° C. as a reference point.
  • organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; Anthraquinone pigments such as pyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; quinophthalone-based pigments; threne-based pigments; and metal complex-based pigments.
  • diketopyrrolopyrrole pigments such as azo, disazo and polyazo
  • phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine
  • Anthraquinone pigments such as pyrimidine, flavan
  • inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum.
  • Dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.
  • the tensile breaking strength of the polyimide film is preferably 60 MPa or more, more preferably 120 MPa or more, and still more preferably 160 MPa or more. Although the upper limit of the tensile strength at break is not particularly limited, it is practically less than about 1000 MPa. When the tensile strength at break is 60 MPa or more, it is possible to prevent the polyimide film from breaking when it is peeled off from the inorganic substrate.
  • the method for measuring the tensile strength at break of the polyimide film is according to the method described later.
  • the two directions perpendicular to and parallel to the application of the casting applicator were defined as (MD direction) and (TD direction), respectively. The same applies to the following tensile elongation at break and tensile modulus.
  • the polymer film of the present invention is preferably a polyimide film having a breaking elongation of preferably 3% or more, preferably 5% or more, more preferably 7% or more, and still more preferably 9% or more.
  • the breaking elongation is also a measure of the bending property. If the breaking elongation is low, the film is brittle and easily cracked, so the film may crack during bending, but bending is possible if the breaking elongation is 5% or more.
  • a polyimide film having an elastic modulus of preferably 3 GPa or more, more preferably 4 GPa or more, still more preferably 5 GPa or more, particularly preferably 7 GPa or more, preferably 15 GPa or less, more preferably 12 GPa or less is used as the polymer film. It is preferable to use When the elastic modulus is within this range, the board can be bent at the edges and the damage to the wiring can be minimized. If the modulus of elasticity is lower than this range, the polymer film will be greatly deformed when it is folded, which may cause disconnection of the wiring. On the other hand, if the elastic modulus is too high, it may become difficult to bend.
  • the tensile product which is the product of tensile strength and elongation, is improved compared to conventional polyimide films. That is, the tensile product in the tensile test of the polyimide film of the present invention is preferably 300 MPa ⁇ % or more, more preferably 1,000 MPa ⁇ % or more, and even more preferably 1,200 MPa ⁇ % or more. . Although the upper limit is not particularly set, the tensile product in a tensile test is preferably 20,000 MPa ⁇ % or less from the viewpoint of the handleability of the film. The tensile product may be, for example, 18,000 MPa ⁇ % or less, 15,000 MPa ⁇ % or less, or 10,000 MPa ⁇ % or less.
  • the compressive strength of the polymer film in order to bend the polymer film along the side surface of the substrate without stress, it is preferable to adjust the compressive strength of the polymer film to be weaker than the tensile strength of the polymer film.
  • voids are intentionally formed in the polymer film to facilitate buckling against compressive stress.
  • 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 its production. Morphology is more preferred. When the polyimide film is wound into a roll, the polyimide film wound into a roll can be easily transported.
  • a lubricant particles having a particle diameter of about 10 to 1000 nm is added and contained in the polyimide film in an amount of about 0.03 to 3% by mass. It is preferable to provide the surface of the polyimide film with fine irregularities to ensure slipperiness.
  • the CTE difference between the first polyimide film layer in contact with the inorganic substrate and the second polyimide film layer adjacent to the first polyimide film without contacting the inorganic substrate is preferably 40 ppm/K or less. , more preferably 30 ppm/K or less, and still more preferably 15 ppm/K or less.
  • the thickest layer of the second polyimide film has a thickness within the above range.
  • the polyimide film has a symmetrical structure in the film thickness direction because warping is less likely to occur.
  • the first polyimide film layer in contact with the inorganic substrate and the second polyimide film layer adjacent to the first polyimide film layer (hereinafter simply referred to as "second The thickness of the mixture at the interface with the second polyimide film layer)) is less than the sum of the thickness of one layer of the first polyimide film layer and the thickness of one layer of the second polyimide film layer.
  • second The thickness of the mixture at the interface with the second polyimide film layer is less than the sum of the thickness of one layer of the first polyimide film layer and the thickness of one layer of the second polyimide film layer.
  • the lower limit is not particularly limited, but industrially, there is no problem if it is 10 nm or more, and it may be 20 nm or more.
  • Means for forming a layer with less mixing is not particularly limited, but rather than simultaneously producing two layers of the first polyimide film layer and the second polyimide film layer by solution casting, the first polyimide film layer or It is preferable to fabricate any one layer of the second polyimide film layer and fabricate the next layer after passing through the heating step. It includes both the intermediate stage and the completed heating process. It is better to make the next layer after the heating process is completed, but the finished film surface often has already lost reactivity, and since there are few functional groups on the surface, it is difficult to separate the two layers. Poor adhesive strength may cause problems in practical use. Therefore, even if there is little mixing, it is desirable to have an interface where the mixing occurs at a thickness of 10 nm or more.
  • the polymer compositions of the first polyimide film layer and the second polyimide film layer may be the same or different.
  • simultaneous coating by a T-die capable of simultaneous ejection of two or more layers, sequential coating in which one layer is coated and then the next layer is coated, and one layer is coated.
  • various existing coating methods and multi-layering techniques can be appropriately adopted.
  • a laminated body in which a substrate and a polymer film are adhered is passed through during the process.
  • a film lamination method and a varnish method can be exemplified as methods for obtaining such a laminate.
  • a laminate is obtained by bonding a polymer film and a substrate together with an adhesive or a pressure-sensitive adhesive.
  • Epoxy-based adhesives, silicone-based adhesives, acrylic-based adhesives, and adhesives can be used as adhesives.
  • a highly heat resistant adhesive when a high temperature process is applied to the formation of the electronic display device, it is necessary to use a highly heat resistant adhesive.
  • a highly heat-resistant bonding method a method of bonding a substrate and a polymer film via a silane coupling agent condensate can be used.
  • the substrate is also required to have heat resistance, so it is preferably used in combination with an inorganic substrate, preferably a glass substrate.
  • the silane coupling agent may be applied to the adhesive surface of either or both of the polymer film and the substrate, and the two may be superimposed and heated.
  • the organic groups of the silane coupling agent react with the surface of the polymer film, the methoxy and ethoxy groups of the silane coupling agent react with the hydroxyl groups on the surface of the inorganic substrate, and the silane coupling agents self-condense to form a condensate layer. is formed to perform adhesion.
  • this method for example, by combining with the technology disclosed in Japanese Patent No. 5224011, it is possible to control the adhesive strength and form a pattern of portions with strong adhesive strength and weak portions. and the polymer film can be partially peeled off.
  • a polymer film is obtained by coating a substrate with a resin solution or a polymer precursor solution that constitutes the polymer film, drying it on the substrate, and performing a chemical reaction as necessary.
  • a typical example is the use of a polyimide resin solution or a polyamic acid solution, which is a polyimide precursor, to obtain a polyimide film.
  • the method disclosed in Japanese Patent No. 5862866 can be used to control the adhesive force between the substrate and the polymer film, and to form portions with strong adhesive strength and portions with weak adhesive strength in a pattern. It is possible.
  • the properties of the polymer film defined in the present invention are obtained by the following methods.
  • thickness of polymer film > The thickness of the polymer film was measured using a micrometer (“Millitron 1245D” manufactured by Fineruff Co.), and the average value of 10 points was obtained.
  • ⁇ Tensile modulus, tensile strength at break and tensile elongation at break of polymer film From the polymer film to be measured, a strip-shaped test piece having a flow direction (MD direction) and a width direction (TD direction) of 100 mm ⁇ 10 mm was cut out, and a tensile tester (Shimadzu Corporation "Autograph (Registered Trademark); model name AG-5000A"), tensile modulus, tensile strength at break, and tensile elongation at break were measured in each of the MD and TD directions under conditions of a tensile speed of 50 mm/min and a distance between chucks of 40 mm. , the mean value of all measurements taken in the MD and TD directions was obtained.
  • MD direction flow direction
  • TD direction width direction
  • the glass transition temperature was measured at 30° C. using a dynamic viscoelasticity measuring device (DMA: manufactured by UBM, trade name: E4000F) using a polymer film (eg, polyimide film) having a size of 5 mm ⁇ 20 mm. Measurement was carried out at a temperature increase rate of 4°C/min from 400°C to 400°C at a frequency of 1 Hz, and the temperature at which the change in elastic modulus (mechanical tan ⁇ ) was maximum was taken as the glass transition temperature.
  • DMA dynamic viscoelasticity measuring device
  • E4000F dynamic viscoelasticity measuring device
  • CTE Linear expansion coefficient of polymer film>
  • MD direction machine direction
  • TD direction width direction
  • the expansion ratio was measured under the following conditions, and the expansion ratio was measured at intervals of 15 ° C. (30 ° C. to 45 ° C., 45 ° C. to 60 ° C., ...) was measured, this measurement was performed up to 300°C, and the average value of all the measured values measured in the MD and TD directions was calculated as the coefficient of linear expansion (CTE).
  • Atmosphere Argon Initial load: 34.5 g/mm2
  • Total light transmittance The total light transmittance (TT) of the film was measured using a Hazemeter (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.
  • the silane coupling agent condensate layer 20 is literally a layer made of a silane coupling agent condensate.
  • the silane coupling agent layer has a function of bonding the substrate and the polymer film. Part or all of the bonding surfaces of the polymer film and the substrate are bonded via the silane coupling agent condensate layer.
  • the silane coupling agent condensate layer is preferably present on the first surface and/or the second surface of the substrate, more preferably present on the first surface and the second surface of the substrate. preferable. Moreover, it is more preferable to exist on the entire first surface and the entire second surface of the substrate.
  • silane coupling agents organicize the surfaces of inorganic substances through a dealcoholization condensation reaction between hydroxyl groups present mainly on the surfaces of inorganic substances and methoxy groups, ethoxy groups, etc. contained in the molecules of the silane coupling agents. It is a general term for compounds. Such a dealcoholization reaction also occurs between silane coupling agents, resulting in a condensate in which the silane coupling agents are linked by siloxane bonds.
  • the silane coupling agent is preferably a compound containing 10% by mass or more of Si (silicon) component. Furthermore, it is preferable to have an alkoxy group in the structure.
  • silane coupling agents that can be preferably used in the present invention 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, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-
  • silane coupling agents having one silicon atom in one molecule are particularly preferred, for example, 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, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane and the like. If the process requires particularly high heat resistance, it is desirable to have an aromatic group connecting Si and an amino group. As the coupling agent, 11
  • the silane coupling agent is generally liquid, and a layer is obtained by coating it on a substrate or polymer film.
  • a coating method a vapor phase coating method such as a wet coating method or a vapor deposition method can be used.
  • spin coating, curtain coating, dip coating, slit die coating are performed using a silane coupling agent undiluted solution or a solution diluted with a solvent such as an alcohol solution or aqueous solution.
  • a gravure coating method, a bar coating method, a comma coating method, an applicator method, a screen printing method, a spray coating method, and the like can be appropriately used.
  • a drawing application using a dispenser, a dropper, or a brush can also be used.
  • the silane coupling agent layer can be applied via a vapor phase like vapor deposition.
  • the substrate or polymer film is formed by exposing it to the vapor of the silane coupling agent, ie, the silane coupling agent in a substantially gaseous state.
  • the vapor of the silane coupling agent can be obtained by heating the silane coupling agent in a liquid state to a temperature from 40° C. to about the boiling point of the silane coupling agent.
  • the boiling point of the silane coupling agent varies depending on the chemical structure, but generally ranges from 100 to 250°C. However, heating at 200° C. or higher is not preferable because it may cause a side reaction on the organic group side of the silane coupling agent.
  • the silane coupling agent may be applied to both surfaces of the substrate and the polymer film.
  • the wiring 40 of the present invention is a wiring formed on the surface of the polymer film 30 opposite to the bonding surface with the substrate 15 and extending from the first surface side to the second surface side of the substrate, preferably.
  • the wiring is actually stretched like a mesh in the electronic display device, and has a multi-layered wiring structure. Only the part placed in the .
  • the wiring is preferably a metal layer, and is mainly made of copper, silver, aluminum, gold, silver, nickel, chromium, tin, lead, etc., which have high conductivity, or molybdenum, tungsten, etc., which have a low coefficient of linear expansion. Used.
  • Alloys such as brass, cupronickel, bronze, invar, stainless steel, and solder may also be used as necessary.
  • Such wiring is formed by a vacuum metallizing technique such as vapor deposition or sputtering, a wet metallizing technique such as electroless plating, or a metallizing technique such as plasma spraying, either singly or in combination.
  • the wiring is patterned by etching, masking, or the like. Although omitted in the drawing for simplification, it is preferable that the wiring is insulated and protected by resin or the like. Insulating protection is preferably applied to the top surface, bottom surface, and side surfaces of the wiring.
  • the drive circuit element (driver IC) 50 of the electronic display device is an integrated electronic circuit element that supplies image signals and power to the electronic display device.
  • a conventional semiconductor element may be used for the driver IC, and it is preferable that the driver IC be mounted in the form of a bare chip.
  • the driver IC 50 is preferably mounted on the surface opposite to the electronic device 60. In FIG. 1, it is mounted (mounted) on the surface of the polymer film that is adhered to the second surface of the inorganic substrate.
  • connection bumps or the like are formed on electrode portions extending from the wiring. In the case of face-up wiring, surface treatment suitable for wire bonding is applied to the wiring.
  • a method of TAB bonding using the wiring as flying leads can also be used. It is a preferred embodiment to perform surface treatment of the wiring by gold plating, tin plating, or the like. After mounting the driver IC, an underfill agent, overcoat, or pod sealing may be applied.
  • the electronic display device 60 in the present invention refers to an electronic display device generally called FPD: flat panel display, such as a liquid crystal display device, an OLED (organic EL element), a micro LED array, an electrophoretic display, etc.
  • FPD flat panel display
  • OLED organic EL element
  • micro LED array a micro LED array
  • electrophoretic display etc.
  • CRT cathode-ray tube
  • the present invention is preferably combined with a technique for increasing the area by tiling, and can be combined with a reflective display device such as a self-luminous OLED, a micro LED array, an electrophoretic electronic display device, or a reflective liquid crystal display device. preferable.
  • the electronic display device 60 is preferably formed on the side opposite to the driver IC 50, and in FIG. non-adhesive side). That is, it is preferably constructed on the polymer film surface.
  • An electronic display device generally consists of a backplane and a frontplane. The following process is illustrated as an example of forming an electronic display device according to the present invention. First, after forming a gas barrier film, an anchor layer, etc., on the non-adhesive side surface of the polymer film adhered to the substrate, as necessary, thin-film semiconductor elements and pixel drive electrodes, etc., which directly handle each pixel signal, are formed.
  • a front plane equipped with a facing electrode or, if necessary, a color filter, etc. is formed in a build-up manner, or a separately prepared front plane is attached.
  • Electronic display devices are collections of individual pixels (picture elements).
  • the pixel dimension of the electronic display device (hereinafter also referred to as pixel size or pixel dimension) is defined as Lpx. Pixel dimensions can be determined in either the X or Y direction by dividing the dimensions of the electronic display device in either direction by the number of pixels comprising the same direction.
  • the adhesive layer 70 when it is necessary to bond the polymer film and the substrate without using a silane coupling agent, they may be bonded with an adhesive to form the adhesive layer 70 .
  • the adhesive it is preferable to use an adhesive having relatively high heat resistance, such as epoxy resin or silicone resin, which is generally used in the field of electronics.
  • the adhesive preferably has a Si (silicon) component content of less than 10% by mass. Furthermore, it is preferable that it does not have an alkoxy group in its structure.
  • the casting resin 90 fills the gap with the resin, so that the polymer film located on the side surface of the substrate is formed. It fixes and indirectly protects the wiring formed on the polymer film.
  • Epoxy resins, acrylic resins, silicone resins, urethane resins, phenol resins, melamine resins, and the like can be used as casting resins.
  • Process A in FIG. 8 is the substrate 15 before processing.
  • Step B in FIG. 8 shows a state in which the silane coupling agent condensate layer 20 is formed on the surface of the substrate 15 .
  • the silane coupling agent is not completely condensed in this state.
  • Process C of FIG. 8 is a state in which a polymer film 30 is further adhered.
  • the adhesive surface of the polymer film is preferably chemically activated by plasma treatment or the like, that is, in a state in which highly chemically active functional groups such as carboxyl groups, hydroxyl groups, amino groups, and carbonyl groups are present. preferable.
  • the organic portion of the silane coupling agent reacts with the functional group, and the methoxy group and ethoxy group of one silane coupling agent undergo a dealcoholization reaction and react with hydroxyl groups on the surface of the substrate to bond the two.
  • the silane coupling agents also condense to form a condensate layer.
  • Steps A to C correspond to "(a) a step of preparing a laminate having a substrate and a polymer film adhered to at least one side of the substrate".
  • step E of FIG. 8 an electronic display device is formed. The wires actually extend in a mesh within the electronic display device. Steps D and E correspond to "(b) the step of forming an electronic display device and wiring on a polymer film".
  • step F of FIG. 8 a portion of the substrate corresponding to the wiring area is removed, and the laminate is divided into the display area X1 and the wiring area X2 by this step. More strictly, the size of the display area of the electronic display device and the size of the remaining substrate are preferably the same, or the size of the substrate is smaller than the size corresponding to the thickness of the substrate. preferably. As a result, the polymer film serving as the wiring region surrounds the electronic display device in a frame shape. In order to remove a predetermined portion of the substrate, the substrate may be cut mechanically or by laser irradiation or the like, or divided after creating a notch. In the case of a metal substrate, it is also possible to remove the corresponding portion by etching.
  • This step F is "(c) a step of removing the substrate outside the area where the electronic display device is formed and dividing it into a display area adhered to the substrate and a wiring area from which the substrate has been removed". corresponds to
  • Step G1 in FIG. 9(A) represents a state in which a slit 31 is formed in the polymer film surrounding the periphery of the electronic display device from the opposite side of the wiring side.
  • the slit can be cut halfway through the polymer film or up to the boundary between the polymer film and the wiring.
  • the slits are drawn at an acute angle in the drawing, but if a slit having an opening of 90 degrees is inserted, the polymer film can be bent at right angles at the slits.
  • Step G1 or G2 is performed to enable the polymer film to be bent at an acute angle and to minimize damage to the wiring when the polymer film is folded. Either one of slit formation and thinning may be used, or both may be used in combination as appropriate.
  • Process H in FIG. 9A shows the case where the wiring is thinned by process G2.
  • a silane coupling agent 21 is applied in advance to the portion of the second surface (rear surface) of the substrate where the folded polymer film contacts. In this case, a required amount may be applied to a required portion using a dispenser or the like. It can also be applied in the laboratory using a dropper or paintbrush. Step I in FIG.
  • FIG. 9A shows a state in which the polymer film is folded and the corresponding portion of the polymer film is adhered to the second surface (rear surface) of the substrate via the silane coupling agent layer. Also in this case, similarly to steps A to C, the reaction of the silane coupling agent to bond the substrate and the polymer film and the reaction of self-condensation proceed in parallel to form a silane coupling agent layer.
  • J in FIG. 9A shows a state in which the drive circuit element (driver IC) of the electronic display device is mounted.
  • the configuration shown in FIG. 1A is obtained. Even when two 90-degree slits are provided, the configuration shown in FIG. 1(A) is obtained schematically.
  • the polymer film is adhered to the inorganic substrate, the electronic display device portion is not peeled off from the inorganic substrate, and the inorganic substrate portion used for manufacturing is incorporated into the electronic display device. It is also possible to peel off the entire polymer film from the inorganic substrate, prepare a new substrate of a predetermined size, reattach it, and proceed to step F.
  • FIG. 2(A) shows a case where an adhesive is used instead of the silane coupling agent in steps H to I of FIG. 9(A).
  • the silane coupling agent layer is extremely thin, so the inorganic substrate, which can be regarded as a rigid body, effectively supports the polymer film directly. form.
  • the elastic layer that supports the wiring is only the polymer film layer, and the heat, pressure, and ultrasonic vibrations during bonding are not absorbed more than necessary, and as a result, bonding with a low defect rate can be performed.
  • the elastic layer consists of two layers, the polymer film and the adhesive layer, which tends to attenuate ultrasonic vibrations during bonding.
  • the entire device is ultrasonically sensitive.
  • FIG. 3A shows the case where the polymer film is adhered to the inorganic substrate using an adhesive instead of the silane coupling agent in step B.
  • FIG. 4 shows a state in which the side portions of the polymer film and the inorganic substrate are also adhered by the silane coupling agent condensate.
  • the side faces of the display devices are easily damaged, so it is one of the preferable aspects to securely adhere and fix the side faces to the inorganic substrate. If a silane coupling agent is also applied to the side surface of the inorganic substrate in step H, and the polymer film is bent along the side surface of the inorganic substrate, the structure shown in FIG. can be realized.
  • a silane coupling agent or a silane coupling agent solution 21 is applied to part or all of the back side (second surface) of the remaining substrate.
  • a required amount may be applied to a required portion using a dispenser or the like. It can also be applied in the laboratory using a dropper or paintbrush. When a solution is used, it is dried to form a silane coupling agent film.
  • step H of FIG. 9(B) a portion of the polymer film in the wiring region adjacent to the display region is heated, then the polymer film is folded along with the wiring along the side surface (cut surface) of the substrate, Further, it is bent toward the back side (second surface) of the substrate.
  • This process consists of "(d) heating the vicinity of the boundary between the display area and the wiring area to a temperature equal to or higher than the softening point of the polymer, and bending the wiring area along the side surface of the substrate; It corresponds to the step of bending from the back toward the back surface (second surface).
  • a silane coupling agent 21 is applied in advance to the second surface (rear surface) of the substrate. Each reacts and adheres to the substrate.
  • Heating methods for polymer films include irradiation with ultraviolet rays, infrared rays, laser light, or strong flash lamps, direct contact with heated objects, heating by radiant heat by bringing heated objects close to each other, and electromagnetic induction on the wiring itself.
  • a heating method, a heating method using microwaves, or the like can be appropriately selected and used.
  • the heating temperature is preferably in the range from the softening temperature of the polymer film to the softening temperature +80°C.
  • Step I in FIG. 9B shows a state in which the polymer film is folded and the corresponding portion of the polymer film is adhered to the second surface (rear surface) of the substrate via the silane coupling agent layer.
  • the silane coupling agent is used, but an adhesive may be used instead of the silane coupling agent.
  • J in FIG. 9B shows a state in which the drive circuit element (driver IC) of the electronic display device is mounted.
  • an electronic display device having a side surface illustrated schematically in FIG. 1B and specifically illustrated in FIG. 14 can be obtained.
  • the polymer film is adhered to the inorganic substrate, the electronic display device portion is not peeled off from the inorganic substrate, and the inorganic substrate portion used for manufacturing is incorporated into the electronic display device. It is also possible to peel off the entire polymer film from the inorganic substrate, prepare a new substrate of a predetermined size, reattach it, and proceed to step F. From the viewpoint of manufacturing process suitability, it is preferable to use inorganic substrates with high heat resistance in the manufacture of electronic display devices. Using lighter and thinner substrates is one option. FIG.
  • FIG. 2B shows a case where an adhesive is used instead of the silane coupling agent when the polymer film and the substrate are adhered to obtain a laminate in steps B to C.
  • FIG. 3B shows the case where the polymer film is adhered to the second surface of the inorganic substrate using an adhesive instead of the silane coupling agent in steps I to H.
  • FIG. 6 shows a case in which the display area is set larger than the substrate size.
  • FIG. 7 shows a case where there is a gap between the folded polymer film and the side surface of the substrate, and the gap is filled with casting resin 90 .
  • Process A in FIG. 10 is the substrate before processing.
  • step B of FIG. 10 the substrate surface is coated with the polymer solution or polymer precursor solution 35 .
  • the silane coupling agent (layer) is omitted from the figure because it may or may not be used.
  • a silane coupling agent is applied to the substrate and a pretreatment for patterning is performed, followed by a polymer solution or a polymer precursor. Body solution should be applied.
  • steps A to C correspond to "(a) the step of preparing a laminate having a substrate and a polymer film adhered to at least one side of the substrate” in the varnish method. Subsequent steps are generally the same as in the case of using the film lamination method.
  • step D of FIG. 10 wiring is formed on the surface of the polymer film opposite to the adhesive surface (non-adhesive side). Only the peripheral portion is shown for convenience.
  • step E of FIG. 10 an electronic display device is formed. The wires are actually connected to wiring layers arranged in a mesh within the electronic display device.
  • Steps D and E correspond to "(b) the step of forming an electronic display device and wiring on a polymer film" in the varnish method.
  • step F of FIG. 10 a portion of the substrate is removed and divided into a display area X1 and a wiring area X2.
  • Step G1 in FIG. 11A represents a state in which a slit 31 is formed in the polymer film surrounding the electronic display device from the opposite side of the wiring side.
  • Step G2 in FIG. 11A shows a state in which the thinning process is performed from the side opposite to the side on which the wiring of the polymer film surrounding the electronic display device is present. Also in this case, the wiring becomes a so-called flying lead 41 .
  • the polymer film has thermoplasticity, it is possible to locally heat the polymer film portion to a temperature higher than the heat distortion temperature and bend it, as in the case of using the film lamination method.
  • Step H in FIG. 11A shows the case where the film is bent at the side surface without performing the slitting in step G1 and the thinning treatment in step G2.
  • a silane coupling agent 21 is applied in advance to the portion of the second surface (rear surface) of the substrate where the folded polymer film contacts. In this case, a required amount may be applied to a required portion using a dispenser or the like. It can also be applied in the laboratory using a dropper or paintbrush.
  • Step I in FIG. 11A shows a state in which the polymer film is folded and the corresponding portion of the polymer film is adhered to the second surface (rear surface) of the substrate via the silane coupling agent layer.
  • FIG. 11A shows a state in which the drive circuit element (driver IC) of the electronic display device is mounted.
  • the entire polymer film is peeled off from the inorganic substrate at the stage of progressing to step E, and a new substrate of a predetermined size is prepared and re-adhered to proceed to step F.
  • the varnish method is one of the aspects that can be selected.
  • the steps after the step G are the same as those of the film lamination method.
  • the varnish method as in the film lamination method, the entire polymer film is peeled off from the inorganic substrate at the stage of progressing to step E, and a new substrate of a predetermined size is prepared and re-adhered to proceed to step F. is one of the aspects that can be selected.
  • the external dimension Lo of the electronic display device and the external shape Ld of the display section of the electronic display device have the following relationship. Lo ⁇ (1/2) ⁇ (Ld+5 ⁇ Lpx)
  • Lo External dimensions of the electronic display device
  • Ld External dimensions of the display portion of the electronic display device
  • Lpx Pixel dimensions of the electronic display device.
  • Lov 1/2 of the dimension obtained by subtracting the dimension Ld of the area where the image can actually be displayed from the external dimension Lo of the electronic display device is the dimension Lov of the area outside the display area where the image cannot be displayed (overhang portion).
  • Lov can be understood as the minimum width of the picture frame.
  • a preferred feature of the present invention is to set the overhang width to 2.5 times or less of the pixel dimension. If the frame width is about 2.5 times or less than the display pixel, the width of the non-display portion generated when tiling is about 5 times or less than the pixel size, making the tiling seams inconspicuous. It is more preferably 2.4 times or less, still more preferably 2.2 times or less, and particularly preferably 2.0 times or less.
  • Lov is the sum of the wiring thickness Lb and the side gap Lg.
  • the wiring thickness is the sum of the polymer film thickness and the wiring thickness.
  • Lb is the wiring thickness.
  • Both polymer films and wires have a finite flexural modulus. Therefore, the polymer film can be bent with a finite radius of curvature Ri (unless the polymer film is slit, thinned, or temporarily plasticized by heating). In this case the radius of curvature corresponds to the sum of Lg and Lb, ie equal to Lov.
  • FIG. 13 shows a state in which a resin is filled in a gap formed on the side surface of the electronic display device of the present invention.
  • a resin to fix the shape of the polymer film on the side surface
  • the shape of the side surface of the electronic display device of the present invention can be maintained well. If a mold or the like is used during fixation, the side surface shape can be approximated to an ideal shape.
  • FIG. 14 shows a situation where there are substantially no gaps on the sides of the electronic display device of the present invention.
  • the polymer film By partially heating and plasticizing the polymer film, the polymer film can be deformed and processed into such a form. In this case, Lov becomes equal to the total thickness of the polymer film and wiring layer, and the frame width can be made very narrow.
  • FIG. 15 shows the case where there is no gap and the thickness of the polymer film on the side surface of the substrate is reduced. In this case, Lov becomes equal to the wiring thickness.
  • FIG. 16 shows a form in which the display area of the electronic display device is stepped in and removed, and since the outer dimension Lo of the electronic display device and the dimension Ld of the display area of the electronic display device are substantially equal, the frame is eliminated. It becomes possible to
  • FIG. 17 shows a case in which a silane coupling agent is used for adhesion between a polymer film, which is a TAB base material, and the second surface of the substrate in a conventional electronic display device using TAB.
  • the TAB and the electronic display device are connected by an ACF (Anisotropic Conductive Film), and the ACF portion cannot be used for display.
  • ACF Anaisotropic Conductive Film
  • FIG. 18 is a detailed cross-sectional schematic diagram of a side portion of a conventionally proposed electronic display device similar to the present invention. Since the polymer film is bent with a large curvature, the overhang becomes large and it is difficult to narrow the frame width. The reason for such a form is that the polymer film has poor flexibility, and if the curvature is reduced, the possibility of breaking the film increases.
  • PAA1 polyamic acid solution
  • a dispersion obtained by dispersing colloidal silica in dimethylacetamide as a lubricant (“Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries) and silica (lubricant). was added so that the total polymer solid content in the polyamic acid solution was 0.5% by mass) to obtain a polyamic acid solution (V1) containing a lubricant.
  • PAA2 polyamic acid solution
  • a dispersion obtained by dispersing colloidal silica in dimethylacetamide as a lubricant manufactured by Nissan Chemical Industries, Ltd. "Snowtex (registered trademark) DMAC-ST-ZL" and silica (lubricant) was added so that the total polymer solid content in the polyamic acid solution was 0.5% by mass) to obtain a polyamic acid solution (V2) containing a lubricant.
  • PAA4 polyamic acid solution
  • V4 lubricant-containing polyamic acid solution
  • the wetted parts of the vessel equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and the infusion tube are made of austenitic stainless steel SUS316L.
  • p-Aminophenyl)benzoxazole (DAMBO) was introduced.
  • N-methyl-2-pyrrolidone was added and completely dissolved, and then 420 parts by mass and 217 parts by mass of pyromellitic dianhydride (PMDA), SQ1.
  • PMDA pyromellitic dianhydride
  • the contents of the reaction vessel were filtered using a suction filtration device, washed with 10,000 parts by mass of methanol, and filtered to obtain polyimide resin powder.
  • the obtained polyimide resin powder was dried at 50° C. for 24 hours using a dryer equipped with a local exhaust device, and further dried at 260° C. for 2 hours to remove remaining volatile components to obtain a dry polyimide powder. got a body
  • the resulting dry polyimide powder had a reduced viscosity of 5.40 dl/g.
  • 400 parts by mass of the obtained dry polyimide powder was dissolved in 3000 parts by mass of DMAc to obtain a polyimide solution (PI5).
  • Colloidal silica was added in the same manner to obtain a lubricant-containing polyimide solution (V5).
  • the lubricant-containing polyamic acid solution (V1) was fed, coated on a polyethylene terephthalate film support to a final thickness of 25 ⁇ m, and dried at 110° C. for 30 minutes.
  • a polyamic acid film (green film) was obtained by peeling the polyamic acid film, which became self-supporting after drying, from the support.
  • the obtained green film is passed through a continuous heat treatment furnace, and the first stage is heated at 200° C. for 3 minutes, and the second stage is heated at a temperature increase rate of 4° C./second and heated at 420° C. for 5 minutes for 2 hours. Staged heating was applied to drive the imidization reaction.
  • Polyamide acid solutions (V2) and (V3) containing a lubricant and polyimide solution (V5) containing a lubricant are used in the same manner, and a polyimide film F2 is formed from the polyamic acid solution V2 containing a lubricant in the same manner as in (V1).
  • a polyimide film F3 was obtained from V3, and a polyimide film F5 was obtained from the lubricant-containing polyimide solution V5.
  • a green film was similarly prepared, and the temperature was raised at a rate of 4° C./second at 200° C. for 3 minutes, followed by heating at 490° C. for 5 minutes as the second step. to allow the imidization reaction to proceed.
  • polyimide film F4 having a width of 524 mm, a length of about 200 m, and a thickness of 25 ⁇ m only at the central portion.
  • polyamic acid solution V6 a green film was prepared in the same manner, and the temperature was raised at a rate of 4°C/sec at 200°C for 3 minutes, followed by heating at 380°C for 5 minutes as the second step. to allow the imidization reaction to proceed.
  • Table 2 shows a list of properties of the obtained polyimide film. Numerical values in the table are average values in the MD and TD directions. MD is the longitudinal direction during film formation, and TD is the width direction during film formation.
  • a vacuum plasma treatment was performed on the polyimide film F1.
  • the vacuum plasma treatment uses an apparatus for long film treatment, evacuates the vacuum chamber to 1 ⁇ 10 -3 Pa or less, introduces argon gas into the vacuum chamber, discharge power 100 W, frequency 15 kHz. Plasma treatment with argon gas was performed for 20 seconds under these conditions.
  • ⁇ Silane coupling agent treatment of glass substrate> As the glass substrate [G], OM10G manufactured by Nippon Electric Glass Co., Ltd. and having a size of 470 mm ⁇ 370 mm and a thickness of 0.7 mm was used. After purging a chamber equipped with a hot plate and a support base for an inorganic substrate with clean dry nitrogen, a UV/ozone-treated glass substrate is placed on the support base, and the liquid surface is positioned 200 mm below the glass substrate. Place a petri dish filled with a silane coupling agent (3-aminopropyltrimethoxysilane), heat the petri dish to 100° C. on a hot plate, and expose the lower surface of the glass substrate to the silane coupling agent vapor for 3 minutes.
  • a silane coupling agent 3-aminopropyltrimethoxysilane
  • ⁇ Lamination> The plasma-treated surface of the polyimide film is superimposed so that it overlaps the silane coupling agent-treated surface of the glass substrate that has been treated with the silane coupling agent, and is temporarily pressed with a roll laminator.
  • the inorganic substrate side was placed on a heated hot plate so as to be in contact with the hot plate, and heat treatment was performed for 3 minutes to obtain a polyimide film/glass substrate laminate (LF1).
  • the resulting polyimide/glass substrate laminate was stored in an environment of 20 to 25° C. and 65 ⁇ 30% relative humidity.
  • a polyimide film/glass substrate laminate (LF2) was obtained from the film F2 and the glass substrate in the same manner.
  • polyimide film glass substrate laminates (LF3), (LF4), (LF5) and (LF6) were similarly obtained from the films F3, F4, F5 and F6 and the glass substrate.
  • a simulated display panel was produced by the process shown in FIGS. 8 and 9A.
  • the glass substrate corresponds to step A in FIG. 8, the glass substrate treated with the silane coupling agent to step B, and the polyimide film/glass laminate to step C.
  • As the wiring layer 40 a nickel-chromium alloy layer is formed by a sputtering method, a copper thin film is formed by a sputtering method, a thick copper film is formed by a sputtering method, and then an unnecessary portion is removed by etching using an etching resist.
  • a wiring 40 was formed by patterning by an active method.
  • an electrophoresis element driven by a TFT using an amorphous silicon thin film as a semiconductor is formed, the glass substrate is cut by a laser cutter to remove unnecessary portions, and laser processing is performed in step G2 of FIG. 9A.
  • the film was thinned to 20% of its original thickness, and the wiring 40 was bent together with the film to the back side of the glass substrate.
  • a 1% by mass methanol solution of 3-aminopropyltrimethoxysilane is used and dropped onto a predetermined position with a dispenser (for convenience, the display device layer is shown facing upward, but in reality After this process, the operation is turned upside down), the polyimide film that has been dried and then folded is crimped to the back side of the glass substrate following the production of a polyimide film/glass substrate laminate, and then heated to bond.
  • the driver IC was mounted to obtain a simulated panel (PF1).
  • a plurality of (PF1) were prepared in the same manner, arranged in a tile form to increase the area, and an image signal was sent to confirm the display. It was confirmed that there were no particular pixel defects between the simulated panels, and good-quality image display was performed.
  • Process A in FIG. 10 is a glass substrate.
  • a state in which the polyamic acid solution (PAA1) is applied to the glass substrate to a predetermined thickness is the step B, and after drying, the polyimide layer is formed by heating in an inert oven, that is, the polyimide layer/glass substrate laminate (LS1). is obtained in the process C.
  • the same operation as in the film method is performed, and the process proceeds to the step shown in FIG.
  • a simulated panel (PS1) was prepared by operating the above. Also in this case, tiling was performed in the same manner as in the case of the film method, and the display image quality was observed, and it was confirmed that good image quality was obtained.
  • the frame can be narrowed, the defect rate of driver IC mounting is low, and it is preferably applicable to self-luminous devices and reflective devices.
  • a display device suitable for ring applications can be realized.
  • the present invention will greatly contribute to the industrial world as a technique for economically manufacturing large-area display devices.

Abstract

La présente invention permet d'obtenir un procédé de fourniture économique d'un appareil d'affichage électronique à cadre étroit dont la surface peut être augmentée par pavage.　Un appareil d'affichage électronique est caractérisé en ce qu'il comprend : un substrat inorganique ; un film polymère qui est plié de telle sorte que le substrat inorganique y est pris en sandwich, et qui est lié à la fois à une première surface et à une seconde surface du substrat inorganique ; un dispositif d'affichage électronique qui est formé sur une surface de film polymère qui est liée à la première surface du substrat inorganique ; un élément de circuit d'attaque pour le dispositif d'affichage électronique, l'élément de circuit d'attaque étant monté sur une surface de film polymère qui est liée à la seconde surface du substrat inorganique ; et une ligne de câblage qui est formée sur les surfaces de film polymère de façon à connecter électriquement le dispositif d'affichage électronique et l'élément de circuit d'attaque pour le dispositif d'affichage l'un à l'autre. Cet appareil d'affichage électronique est également caractérisé en ce que : le film polymère est un film de polyimide qui est un produit de réaction de copolymérisation d'au moins un acide carboxylique, une diamine et un dérivé de silsesquioxane ; le dispositif d'affichage électronique comporte une partie d'affichage ; et la dimension externe Lo du dispositif d'affichage électronique et la dimension externe Ld de la partie d'affichage du dispositif d'affichage électronique satisfont à l'expression relationnelle présentée ci-dessous.　Lo < (1/2) × (Ld + 5 × Lpx). Dans la formule, Lo représente la dimension externe du dispositif d'affichage électronique ; Ld représente la dimension externe de la partie d'affichage du dispositif d'affichage électronique ; et Lpx représente la dimension de pixel du dispositif d'affichage électronique.
PCT/JP2022/028598 2021-08-02 2022-07-25 Appareil d'affichage électronique WO2023013453A1 (fr)

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123416A1 (fr) * 2007-03-30 2008-10-16 Pioneer Corporation Dispositif d'émission de lumière
JP2011011455A (ja) * 2009-07-02 2011-01-20 Toyobo Co Ltd 積層体およびその製造方法
JP2012107121A (ja) * 2010-11-17 2012-06-07 Mitsui Chemicals Inc 誘電特性に優れた樹脂／金属積層体及び回路用基板
US20120190802A1 (en) * 2011-01-26 2012-07-26 Nexolve Corporation Polyimide polymer from non-stoichiometric components
JP2014075547A (ja) * 2012-10-05 2014-04-24 Panasonic Corp 発光装置
US20140183473A1 (en) * 2012-12-28 2014-07-03 Lg Display Co., Ltd. Flexible display device and method of manufacturing the same
JP2014172978A (ja) * 2013-03-08 2014-09-22 Sumitomo Bakelite Co Ltd 共重合ポリイミド前駆体および共重合ポリイミド
US20160174304A1 (en) * 2014-12-10 2016-06-16 Lg Display Co., Ltd. Flexible display device with multiple types of micro-coating layers
JP2017203061A (ja) * 2016-05-09 2017-11-16 三菱瓦斯化学株式会社 ポリイミド及びポリイミドフィルム
JP2018142018A (ja) * 2013-04-15 2018-09-13 株式会社半導体エネルギー研究所 発光装置及びその作製方法
WO2019167966A1 (fr) * 2018-02-28 2019-09-06 京セラ株式会社 Dispositif d'affichage, subsstrat en verre et procédé de fabrication de substrat en verre
US20190280245A1 (en) * 2018-03-08 2019-09-12 Samsung Display Co., Ltd. Foldable display apparatus and method of manufacturing the same
JP2020502313A (ja) * 2017-09-14 2020-01-23 エルジー・ケム・リミテッド ポリイミド共重合体及びそれを利用したポリイミドフィルム
US20200388784A1 (en) * 2019-06-05 2020-12-10 Samsung Display Co., Ltd. Display device
JP2021056525A (ja) * 2016-11-11 2021-04-08 株式会社ジャパンディスプレイ 表示装置

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123416A1 (fr) * 2007-03-30 2008-10-16 Pioneer Corporation Dispositif d'émission de lumière
JP2011011455A (ja) * 2009-07-02 2011-01-20 Toyobo Co Ltd 積層体およびその製造方法
JP2012107121A (ja) * 2010-11-17 2012-06-07 Mitsui Chemicals Inc 誘電特性に優れた樹脂／金属積層体及び回路用基板
US20120190802A1 (en) * 2011-01-26 2012-07-26 Nexolve Corporation Polyimide polymer from non-stoichiometric components
JP2014075547A (ja) * 2012-10-05 2014-04-24 Panasonic Corp 発光装置
US20140183473A1 (en) * 2012-12-28 2014-07-03 Lg Display Co., Ltd. Flexible display device and method of manufacturing the same
JP2014172978A (ja) * 2013-03-08 2014-09-22 Sumitomo Bakelite Co Ltd 共重合ポリイミド前駆体および共重合ポリイミド
JP2018142018A (ja) * 2013-04-15 2018-09-13 株式会社半導体エネルギー研究所 発光装置及びその作製方法
US20160174304A1 (en) * 2014-12-10 2016-06-16 Lg Display Co., Ltd. Flexible display device with multiple types of micro-coating layers
JP2017203061A (ja) * 2016-05-09 2017-11-16 三菱瓦斯化学株式会社 ポリイミド及びポリイミドフィルム
JP2021056525A (ja) * 2016-11-11 2021-04-08 株式会社ジャパンディスプレイ 表示装置
JP2020502313A (ja) * 2017-09-14 2020-01-23 エルジー・ケム・リミテッド ポリイミド共重合体及びそれを利用したポリイミドフィルム
WO2019167966A1 (fr) * 2018-02-28 2019-09-06 京セラ株式会社 Dispositif d'affichage, subsstrat en verre et procédé de fabrication de substrat en verre
US20190280245A1 (en) * 2018-03-08 2019-09-12 Samsung Display Co., Ltd. Foldable display apparatus and method of manufacturing the same
US20200388784A1 (en) * 2019-06-05 2020-12-10 Samsung Display Co., Ltd. Display device

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