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WO2011033751A1 - Polyimide thermoplastique transparent et substrat transparent le contenant - Google Patents

Polyimide thermoplastique transparent et substrat transparent le contenant Download PDF

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Publication number
WO2011033751A1
WO2011033751A1 PCT/JP2010/005551 JP2010005551W WO2011033751A1 WO 2011033751 A1 WO2011033751 A1 WO 2011033751A1 JP 2010005551 W JP2010005551 W JP 2010005551W WO 2011033751 A1 WO2011033751 A1 WO 2011033751A1
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Prior art keywords
polyimide
structural unit
general formula
transparent
formula
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PCT/JP2010/005551
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English (en)
Japanese (ja)
Inventor
岡崎真喜
山下渉
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to JP2011531783A priority Critical patent/JPWO2011033751A1/ja
Publication of WO2011033751A1 publication Critical patent/WO2011033751A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

Definitions

  • the present invention relates to a transparent thermoplastic polyimide and a transparent substrate containing the same.
  • the transparent substrate of the present invention is particularly suitable as a transparent substrate in a flat panel display (FPD).
  • flat panel displays such as liquid crystal display elements and organic EL display elements
  • glass substrates are widely used as display element substrates.
  • flat panel displays have been reduced in size and weight, and a “thin, light, and unbreakable” material that can replace a glass substrate is required.
  • a transparent composite substrate in which a reinforcing material such as glass cloth and a transparent resin are combined has been studied.
  • the transparent resin is colorless and transparent and that the refractive index difference between the transparent resin and the reinforcing material is as small as possible.
  • epoxy resins, vinylbenzene resins, and the like are used as such transparent resins.
  • a transparent composite substrate a transparent composite substrate obtained by impregnating glass fiber with epoxy resin and curing has been proposed (for example, Patent Documents 1 to 3).
  • a transparent composite substrate obtained by impregnating and curing a glass fiber with a vinylbenzene resin has been proposed (for example, Patent Document 4).
  • transparent resins such as epoxy resins and vinylbenzene resins have insufficient heat resistance and have problems with flexibility.
  • a transparent composite substrate containing a transparent polyimide resin having high heat resistance and flexibility is being studied.
  • a transparent composite substrate containing a transparent polyimide resin a polyimide composite film in which a layered silicate treated with an organic onium ion is dispersed in a polyimide having an alicyclic structure has been proposed (see, for example, Patent Document 5).
  • a polyimide inorganic composite material obtained by reacting an aliphatic polyimide with a silane coupling agent and then adding a silicon alkoxide to cause a sol-gel reaction has been proposed (for example, Patent Document 6).
  • Polyimide resin generally has high heat resistance.
  • an optical material containing a polyimide resin an optical waveguide film in which the refractive index of the core and the clad is controlled by controlling the copolymerization ratio of two or more types of polyimide has been proposed (for example, see Patent Document 7).
  • it is a polyimide resin composition whose refractive index changes by electron irradiation, Comprising: The polyimide resin composition obtained by making an alicyclic hydrocarbon diamine compound and tetracarboxylic dianhydride react is proposed ( For example, Patent Document 8).
  • NBDA norbornanediamine
  • 6FDA 2,2-bis (3, which is an aromatic tetracarboxylic dianhydride containing fluorine atoms , 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride
  • 6FDA 2,2-bis (3, which is an aromatic tetracarboxylic dianhydride containing fluorine atoms , 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride
  • Patent Document 10 a polyimide composite film in which a transparent polyimide resin obtained by reacting norbornanediamine (NBDA) with an alicyclic hydrocarbon tetracarboxylic dianhydride and talc or the like has been proposed (for example, Patent Document 10).
  • NBDA norbornanediamine
  • Patent Documents 3 and 4 also disclose colorless and transparent polyimide resins.
  • conventionally it is difficult to reduce the refractive index difference between the transparent polyimide resin and the reinforcing material while maintaining the heat resistance, so that a transparent composite substrate in which the polyimide resin and the reinforcing material such as glass cloth are combined is obtained. It was difficult.
  • an object of the present invention is to provide a transparent substrate having high transparency and heat resistance.
  • Another object of the present invention is to provide a transparent polyimide resin composition that is colorless and transparent and can accurately control the refractive index without impairing the inherent high heat resistance of the polyimide resin.
  • a first aspect of the present invention relates to the transparent substrate shown below and an image display apparatus including the same.
  • a transparent substrate having a base material (I) containing a transparent thermoplastic polyimide and an inorganic filler, The transparent substrate whose refractive index difference in wavelength 589nm of the said transparent thermoplastic polyimide and the said inorganic filler is 0.010 or less.
  • the transparent thermoplastic polyimide includes a polyimide copolymer including the structural unit ⁇ and the structural unit ⁇ , or includes a mixture of a polyimide including the structural unit ⁇ and a polyimide including the structural unit ⁇ .
  • the refractive index of the polyimide composed of the structural unit ⁇ represented by the following general formula (11) at a wavelength of 589 nm is 1.59 to 1.65, and is represented by the following general formula (12)
  • a in the general formula (11) and B in the general formula (12) are divalent organic groups selected from the following: X in the general formula (11) and Y in the general formula (12) are tetravalent organic groups)
  • X in the general formula (11) is a tetravalent organic group selected from the following:
  • the structural unit ⁇ represented by the general formula (11) is represented by the formula (1a)
  • the structural unit ⁇ represented by the general formula (12) is represented by the formula (2a)
  • the mixing ratio (molar ratio) (1a) :( 2a) of the polyimide containing the structural unit represented by 1a) and the polyimide containing the structural unit represented by the formula (2a) is 5:95 to 30:70
  • the transparent substrate according to any one of [3] to [5].
  • the structural unit ⁇ represented by the general formula (11) is represented by the formula (1a)
  • the structural unit ⁇ represented by the general formula (12) is represented by the formula (2b)
  • the polyimide copolymer Copolymerization ratio (molar ratio) (1a) :( 2b) of the structural unit represented by the formula (1a) and the structural unit represented by the formula (2b) in the coalescence, or the formula (1a) in the polyimide mixture The mixing ratio (molar ratio) (1a) :( 2b) of the polyimide containing the structural unit represented by formula (2b) and the polyimide containing the structural unit represented by formula (2b) is 5:95 to 30:70. , [3] to [5].
  • the substrate (I) further includes a layer (II) containing a second transparent thermoplastic polyimide having substantially the same refractive index as the transparent thermoplastic polyimide and not containing an inorganic filler.
  • the transparent substrate according to any one of [14].
  • the base material (I) has a thickness of 30 ⁇ m to 70 ⁇ m
  • the layer (II) has a thickness of 10 ⁇ m to 100 ⁇ m, and a total thickness of 200 ⁇ m or less.
  • the transparent substrate according to any one of [1] to [16] which is used in an image display device.
  • the transparent substrate according to any one of [1] to [16] which is a display panel substrate of an image display device.
  • An image display device comprising the transparent substrate according to any one of [1] to [16].
  • [20] A step of impregnating the polyamic acid with an inorganic filler and then heat-treating to imidize the polyamic acid to obtain the substrate (I) as the transparent thermoplastic polyimide, A step of laminating a film containing the second transparent thermoplastic polyimide and no inorganic filler on the surface of the substrate (I), and a step of thermally fusing the substrate (I) and the film;
  • the method for producing a transparent substrate according to [15] or [16], comprising: [21] The method for producing a transparent substrate according to [20], wherein the polyamic acid has an E-type mechanical viscosity at 25 ° C. of 300 mPa ⁇ s to 15000 mPa ⁇ s.
  • a transparent polyimide composition comprising a mixture with a polyimide containing a structural unit represented by the general formula (2),
  • the refractive index at a wavelength of 589 nm of the polyimide composed of the structural unit represented by the general formula (1) is 1.59 or more and 1.65 or less
  • the polyimide composed of the structural unit represented by the general formula (2) has a refractive index of 1.52 to 1.55 at a wavelength of 589 nm, and the refractive index of the transparent polyimide composition at a wavelength of 589 nm is 1.
  • the transparent polyimide composition which is 53-1.62.
  • X in the general formula (1) and Y in the general formula (2) are tetravalent organic groups
  • X in the general formula (1) is a tetravalent organic group selected from the following:
  • the structural unit represented by the general formula (1) is represented by the formula (1a)
  • the structural unit represented by the general formula (2) is represented by the formula (2a)
  • the mixing ratio (molar ratio) (1a) :( 2a) of the polyimide containing the structural unit represented by formula (2a) and the polyimide containing the structural unit represented by formula (2a) is 5:95 to 30:70.
  • the transparent polyimide composition according to [22] or [23].
  • the structural unit represented by the general formula (1) is represented by the formula (1a)
  • the structural unit represented by the general formula (2) is represented by the formula (2b)
  • the mixing ratio (molar ratio) (1a) :( 2b) of the polyimide containing the structural unit represented by formula (2b) and the polyimide containing the structural unit represented by formula (2b) is 5:95 to 30:70.
  • a polyamic acid copolymer containing the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4), or a polyamide containing the structural unit represented by the general formula (3) A polyamic acid composition comprising a mixture of an acid and a polyamic acid containing a structural unit represented by the general formula (4), The polyimide obtained by imidizing the polyamic acid composed of the structural unit represented by the general formula (3) has a refractive index of 1.59 to 1.65 at a wavelength of 589 nm, The polyimide obtained by imidizing the polyamic acid composed of the structural unit represented by the general formula (4) has a refractive index of 1.52 or more and 1.55 or less at a wavelength of 589 nm, The polyamic acid composition whose refractive index in wavelength 589nm of the transparent polyimide composition obtained by imidating the said polyamic acid composition is 1.53 or more and 1.62 or less. (X in the general formula (3) and Y in the general formula (4) are
  • transparent polyimide that can precisely control the refractive index without impairing the inherent heat resistance of polyimide is combined with a reinforcing material. For this reason, the transparent substrate of the present invention has high transparency and heat resistance.
  • the transparent polyimide composition of the present invention is colorless and transparent and can accurately control the refractive index without impairing the inherent high heat resistance of the polyimide resin.
  • the transparent substrate of this invention has base material (I) and another layer as needed.
  • the substrate (I) contains a transparent thermoplastic polyimide and an inorganic filler.
  • the inorganic filler can increase the mechanical strength of the transparent substrate and reduce the linear expansion coefficient.
  • the transparent thermoplastic polyimide contained in the substrate (I) is obtained by reacting tetracarboxylic dianhydride and diamine, and is a polyimide homopolymer consisting essentially of one type of structural unit; It includes a polyimide copolymer containing two or more kinds of structural units obtained by reacting an anhydride with a diamine.
  • the substrate (I) may contain two or more types of polyimide homopolymers or polyimide copolymers.
  • the transparent thermoplastic polyimide contained in the substrate (I) is a polyimide co-polymer containing a structural unit ⁇ which gives a transparent polyimide having a high refractive index at a wavelength of 589 nm and a structural unit ⁇ which gives a transparent polyimide having a low refractive index at a wavelength of 589 nm.
  • the polyimide composed of the structural unit ⁇ represented by the following general formula (11) has a high refractive index of 1.59 to 1.65 at a wavelength of 589 nm.
  • the polyimide composed of the structural unit ⁇ represented by the following general formula (12) has a low refractive index of 1.52 to 1.55 at a wavelength of 589 nm.
  • X in the general formula (11) and Y in the general formula (12) are each a tetravalent organic group.
  • a in the general formula (11) and B in the general formula (12) are each a divalent organic group derived from an alicyclic hydrocarbon diamine.
  • the polyimide copolymer may be a random copolymer including a structural unit represented by the general formula (11) and a structural unit represented by the general formula (12), or may be a block copolymer. Good.
  • the total of the number of structural units represented by general formula (11) and the number of structural units represented by general formula (12) is 50% or more with respect to the total number of structural units in the polyimide copolymer. Is preferable, and 80% or more is more preferable.
  • the polyimide containing the structural unit represented by the general formula (11) as a main component in the mixture of polyimides may be a polyimide substantially composed of the structural unit represented by the general formula (11). Ingredients may be included.
  • the polyimide containing the structural unit represented by the general formula (12) as a main component may be a polyimide substantially composed of the structural unit represented by the general formula (12), and may contain a small amount of a copolymer component. .
  • the refractive index of the transparent thermoplastic polyimide contained in the substrate (I) can be precisely controlled by adjusting the molar ratio of the structural unit ⁇ and the structural unit ⁇ .
  • the adjustment may be performed by adjusting the copolymerization ratio of the structural unit ⁇ and the structural unit ⁇ ; or by adjusting the mixing ratio of the polyimide containing the structural unit ⁇ as a main component and the polyimide containing the structural unit ⁇ as a main component.
  • Copolymerization ratio (molar ratio) (11) :( 12) of the structural unit ⁇ represented by the general formula (11) and the structural unit ⁇ represented by the general formula (12) in the polyimide copolymer, or polyimide The mixing ratio (molar ratio) of the polyimide containing the structural unit ⁇ represented by the general formula (11) and the polyimide containing the structural unit ⁇ represented by the general formula (12) (11) :( 12)
  • it can be, for example, 5:95 to 30:70.
  • a polyimide containing a divalent organic group derived from an aliphatic diamine has higher transparency than a polyimide containing a divalent organic group derived from an aromatic diamine.
  • polyimides derived from alicyclic hydrocarbon diamines have low crystallinity and are therefore easily formed into films.
  • a in the general formula (11) and B in the general formula (12) are each preferably a divalent organic group derived from an alicyclic hydrocarbon diamine.
  • a plurality of A may be the same as or different from each other, and a plurality of B may be the same as or different from each other.
  • alicyclic hydrocarbon diamines include cyclobutanediamine, cyclohexanediamine, di (aminomethyl) cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane (norbornane diamine), diaminooxybicycloheptane, diaminomethyloxybicycloheptane (oxanorbornane) Diamine), isophorone diamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) isopropylidene and the like.
  • a of General formula (11) and B of General formula (12) are respectively bivalent organic groups represented by a following formula.
  • a in the general formula (11) and B in the general formula (12) are each preferably a divalent organic group derived from norbornanediamine.
  • polyimide derived from norbornane diamine has high transparency and is not too high in crystallinity, so that the glass transition point does not become too high.
  • norbornanediamine examples include 2,3-diaminomethyl-bicyclo [2.2.1] heptane, 2,5-diaminomethyl-bicyclo [2.2.1] heptane, 2,6-diaminomethyl-bicyclo [ 2.2.1] heptane, 2,7-diaminomethyl-bicyclo [2.2.1] heptane and the like, preferably 2,5-diaminomethyl-bicyclo [2.2.1] heptane, 2, 6-diaminomethyl-bicyclo [2.2.1] heptane.
  • Each norbornane diamine includes stereoisomers.
  • the divalent groups derived from a plurality of norbornanediamines may be the same or different.
  • X in the general formula (11) is preferably selected from tetravalent organic groups represented by the following formula.
  • Z 1 to Z 6 in the following formula are each a single bond, —O—, —S—, —CO—, —COO—, —CH 2 —, —C (CH 3 ) 2 —, —SO 2 —. .
  • a plurality of X may be the same or different.
  • X in the general formula (11) may be a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene Dianhydride, 1,4-bis (3,4
  • X in General formula (11) is a tetravalent organic group chosen from the following.
  • the polyimide composed of the structural unit ⁇ in which X is any of these groups in the general formula (11) has a reasonably high refractive index and glass transition temperature.
  • Y in the general formula (12) is a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride containing a fluorine atom or a tetravalent organic group derived from an alicyclic hydrocarbon tetracarboxylic dianhydride. It can be a group. This is because the polyimide composed of the structural unit ⁇ represented by the general formula (2) has relatively low crystallinity and a low refractive index. A plurality of Y may be the same or different.
  • a polyimide containing a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride containing a fluorine atom has not only a low refractive index but also a small decrease in heat resistance.
  • aromatic tetracarboxylic dianhydrides containing fluorine atoms include 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride and the like are included.
  • a polyimide containing a tetravalent group derived from an alicyclic hydrocarbon tetracarboxylic dianhydride has not only a low refractive index but also high transparency.
  • alicyclic hydrocarbon tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, Bicyclo [2.2.1]
  • Y in General formula (12) is a tetravalent organic group represented by a following formula. This is because not only the low refractive index of the polyimide containing the structural unit ⁇ represented by the general formula (12) but also high transparency can be imparted.
  • the refractive index of the transparent thermoplastic polyimide is adjusted according to the refractive index of the inorganic filler (reinforcing material) to be combined. That is, the refractive index of the transparent thermoplastic polyimide is adjusted so that the refractive index difference from the inorganic filler is as small as possible.
  • the difference in refractive index between the transparent thermoplastic polyimide and the inorganic filler at a wavelength of 589 nm is preferably 0.010 or less, and more preferably 0.005 or less.
  • a glass cloth, which is a general inorganic filler, has a refractive index of about 1.55 to 1.62 at a wavelength of 589 nm.
  • the refractive index of transparent thermoplastic polyimide at a wavelength of 589 nm is preferably about 1.53 to 1.62.
  • the refractive index of the transparent thermoplastic polyimide at a wavelength of 589 nm can be measured at 23 ° C. with an Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.)
  • the refractive index of the transparent thermoplastic polyimide is adjusted by the type of combination of the structural unit ⁇ represented by the general formula (11) and the structural unit ⁇ represented by the general formula (12), the copolymerization ratio, or the mixing ratio. sell.
  • the molar ratio of the structural unit ⁇ represented by the general formula (11) in the polyimide copolymer, or the structure represented by the general formula (11) in the mixture of polyimides may be increased.
  • the molar ratio of the structural unit ⁇ represented by the general formula (12) in the polyimide copolymer, or the general formula (12) in the polyimide mixture is used.
  • the content of polyimide containing the structural unit ⁇ as a main component may be increased.
  • Examples of preferable combinations of the structural unit ⁇ represented by the general formula (11) and the structural unit ⁇ represented by the general formula (12) include the structural unit represented by the formula (1a) and the formula (2a).
  • the mixture with the polyimide containing the structural unit is highly heat resistant and has a low coefficient of linear expansion.
  • a polyimide copolymer containing a structural unit represented by the formula (1a) and a structural unit represented by the formula (2b), or a polyimide containing a structural unit represented by the formula (1a) and the formula (2b) In addition to being able to control the refractive index, the mixture with polyimide containing a structural unit represented by the formula has high transparency.
  • the copolymerization ratio (molar ratio) between the structural unit represented by the formula (1a) and the structural unit represented by the formula (2a) (1a): (2a), or a mixture of polyimides or a mixture of polyimides
  • the mixing ratio (molar ratio) (1a) :( 2a) of the polyimide containing the structural unit represented by the formula (1a) and the polyimide containing the structural unit represented by the formula (2a) is the refraction of the inorganic filler to be combined. Depending on the ratio, it is preferably 5:95 to 30:70.
  • the copolymerization ratio (molar ratio) of the structural unit represented by the formula (1a) and the structural unit represented by the formula (2b) (1a): (2b), or a mixture of polyimides or a mixture of polyimides
  • the mixing ratio (molar ratio) (1a) :( 2b) of the polyimide containing the structural unit represented by the formula (1a) and the polyimide containing the structural unit represented by the formula (2b) is also the refraction of the inorganic filler to be combined. Depending on the ratio, it is preferably 5:95 to 30:70.
  • Mat ratio (molar ratio) (1a) :( 2a) of polyimide containing a structural unit represented by formula (1a) and a polyimide containing a structural unit represented by formula (2a) in a mixture of polyimides Means the ratio of the number of structural units represented by Formula (1a) to the number of structural units represented by Formula (2a) of the polyimide contained in the mixture.
  • the mixing ratio (molar ratio) of the polyimide containing the structural unit represented by formula (1a) and the polyimide containing the structural unit represented by formula (2b) (1a) :( 2b ") refers to the ratio of the number of structural units represented by formula (1a) to the number of structural units represented by formula (2b) of the polyimide contained in the mixture.
  • the polyimide copolymer may further include a structural unit other than the structural unit ⁇ represented by the general formula (11) and the structural unit ⁇ represented by the general formula (12).
  • the polyimide mixture includes a polyimide containing a structural unit ⁇ represented by the general formula (11) as a main component and a polyimide other than a polyimide containing a structural unit ⁇ represented by the general formula (12) as a main component. May further be included.
  • the glass transition temperature of the transparent thermoplastic polyimide is preferably 180 to 300 ° C. This is because the transparent thermoplastic polyimide is imparted with a certain level of high heat resistance. Moreover, although the decomposition temperature of a polyimide may exceed 300 degreeC, it is preferable to have a glass transition temperature below a decomposition temperature.
  • the glass transition temperature of the transparent thermoplastic polyimide can be measured using a Shimadzu Corporation TGA-50 at a rate of temperature increase of 5 ° C./min.
  • the inorganic filler contained in the substrate (I) is not particularly limited as long as it does not lower the total light transmittance in the transparent substrate to less than 80%.
  • the inorganic filler may be fibrous or powdery.
  • the average particle diameter of the powdery inorganic filler is, for example, 2 ⁇ m or less.
  • inorganic filler examples include glass filler, silica, alumina and the like.
  • glass filler examples include glass cloth, glass fiber, glass nonwoven fabric, and glass fine particles.
  • the refractive index of the glass cloth is preferably 1.55 to 1.61.
  • the glass cloth include E glass (non-alkali glass), S glass, D glass, NE glass, quartz, high dielectric constant glass, etc., preferably E glass. This is because the refractive index of transparent thermoplastic polyimide is likely to approach the refractive index of E glass.
  • the weaving method of the glass cloth is not particularly limited, and may be plain weave, twill weave, satin weave, tangle weave, double weave or the like.
  • the thickness of the glass cloth contained in the substrate (I) is, for example, about 30 to 300 ⁇ m, preferably 10 to 100 ⁇ m, although it depends on the use of the transparent substrate.
  • the surface roughness of the transparent substrate can be reduced by reducing the single yarn diameter of the glass cloth or substantially eliminating the gap between adjacent yarns (increasing the density of the glass cloth). it can.
  • the average single yarn diameter of the glass cloth is preferably 3.5 to 7.0 ⁇ m.
  • the content of the transparent thermoplastic polyimide in the transparent substrate is preferably 90 to 250 parts by mass, more preferably 90 to 150 parts by mass with respect to 100 parts by mass of the inorganic filler.
  • the base material (I) may further contain other thermoplastic resins or thermosetting resins, various additives, etc. other than the transparent thermoplastic polyimide, as long as the transparency and the controllability of the refractive index are not impaired.
  • various additives include surface treatment agents such as silane coupling agents, borane coupling agents, titanate coupling agents, and aluminum coupling agents. This is because the inorganic filler and the polyamic acid (which is a precursor of the transparent thermoplastic polyimide) are easily adapted.
  • the transparent substrate of the present invention may have a base material (I) and an arbitrary layer (II) laminated thereon.
  • the arbitrary layer (II) preferably contains a transparent thermoplastic polyimide (second transparent thermoplastic polyimide) as a main component and does not contain an inorganic filler.
  • the optional layer (II) preferably reduces the surface roughness of the transparent substrate and suppresses light reflection.
  • the optional layer (II) may be laminated on one side of the substrate (I) or both sides of the substrate (I); the substrate (I) is laminated on both sides of the optional layer (II) Also good. There may be a plurality of base materials (I) and arbitrary layers (II).
  • the 2nd transparent thermoplastic polyimide contained in arbitrary layers (II) has a refractive index equivalent to the transparent thermoplastic polyimide contained in a base material (I).
  • the refractive index difference at a wavelength of 589 nm between the second transparent thermoplastic polyimide and the transparent thermoplastic polyimide contained in the substrate (I) is preferably 0.010 or less, more preferably 0.005 or less. preferable.
  • the second transparent thermoplastic polyimide contained in the arbitrary layer (II) has substantially the same composition as the transparent thermoplastic polyimide contained in the base material (I). Since there is no difference in refractive index between the transparent thermoplastic polyimide contained in the substrate (I) and the transparent thermoplastic polyimide contained in the optional layer (II), the transparency of the transparent substrate is not lowered and the substrate (I ) And the optional layer (II).
  • the content of the second transparent thermoplastic polyimide in the arbitrary layer (II) is preferably 80% by mass or more, and more preferably 95% by mass or more.
  • the thickness of the substrate (I) is preferably 30 ⁇ m to 70 ⁇ m, although it depends on the use of the transparent substrate.
  • the thickness of the optional layer (II) is preferably 10 ⁇ m to 100 ⁇ m. In view of reducing the surface roughness of the transparent substrate, the arbitrary layer (II) may be thinner.
  • the total thickness of the transparent substrate can be, for example, 40 ⁇ m to 200 ⁇ m.
  • the surface roughness of the transparent substrate is preferably small.
  • the surface roughness of the transparent substrate can be measured as Rmax with a surface roughness meter.
  • the single yarn diameter of the glass cloth contained in the substrate (I) is reduced, or the gap between adjacent yarns is substantially eliminated (glass The density of the cloth is increased); or an arbitrary layer (II) may be laminated on the substrate (I).
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the transparent substrate of the present invention.
  • the transparent substrate 10 includes a base material 12 and a pair of layers 14 and 14 ′ laminated on the surface thereof.
  • the base material 12 is a base material (I) containing the aforementioned inorganic filler.
  • the pair of layers 14 and 14 ' is a layer (II) mainly composed of the second transparent thermoplastic polyimide that does not contain the above-described inorganic filler.
  • the pair of layers 14 and 14 ′ can smooth the unevenness of the surface of the transparent substrate and suppress light reflection.
  • the transparent polyimide composition contained in the pair of layers 14 and 14 ′ and the transparent polyimide composition contained in the substrate 12 only have to have the same refractive index.
  • the thickness of the layers 14 and 14 ' is preferably the same. This is to make it difficult for the transparent substrate to warp at high temperatures.
  • the transparent substrate 10 shown in FIG. 1 includes, for example, a) a step of obtaining a base material (I); b) a step of laminating a polyimide film to be a layer (II) on the base material (I); and c) a group It is obtained by a method including a step of thermally fusing the material (I) and the layer (II).
  • step a) polyamic acid is impregnated with an inorganic filler such as glass cloth.
  • the polyamic acid is a precursor solution of transparent thermoplastic polyimide contained in the base material (I).
  • the polyamic acid is imidized by heat treatment at 200 to 270 ° C. for about 2 to 6 hours.
  • the base material (I) containing transparent thermoplastic polyimide and an inorganic filler is obtained.
  • the E-type mechanical viscosity of the polyamic acid at 25 ° C. is preferably 300 mPa ⁇ s to 15000 mPa ⁇ s, and more preferably 300 mPa ⁇ s to 1000 mPa ⁇ s. If E type mechanical viscosity is the said range, it will be excellent in the impregnation property to a glass cloth etc.
  • the E type mechanical viscosity can be measured using a rotor No. 4 with an E type measuring instrument (TVH-22H) manufactured by Toki Sangyo Co., Ltd.
  • Examples of the impregnation method of polyamic acid into glass cloth and the like include a pressure impregnation method and a pressure impregnation method.
  • the pressure impregnation method includes a method in which a glass cloth coated with polyamic acid or a glass cloth immersed in polyamic acid is sandwiched between a pair of substrates and pressed.
  • a polyimide film to be the layer (II) is laminated on the base material (I).
  • the polyimide film to be the layer (II) is obtained by casting the polyamic acid, which is a precursor thereof, on a glass plate, drying and heating (imidizing), and then peeling off the glass plate.
  • step c) the base material (I) and the polyimide film to be the layer (II) are heat-sealed by a hot press machine or the like.
  • the heat fusion temperature is about 200 to 320 ° C., although it depends on the type of transparent thermoplastic polyimide contained in the substrate (I) or layer (II).
  • the pressing pressure is about 5 to 10 MPa, and the pressing time is about 10 to 30 minutes.
  • the light transmittance in the visible light region having a wavelength of 550 nm or more is preferably 80% or more.
  • the light transmittance in the visible light region can be measured by Multi-spec-1500 manufactured by Shimadzu Corporation.
  • the total light transmittance of the transparent substrate is preferably 80% or more, and more preferably 90% or more.
  • the haze of the transparent substrate is preferably 20% or less, and more preferably 10% or less.
  • the total light transmittance and haze of the transparent substrate can be measured by NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the light transmittance in the visible light region of the transparent substrate can be increased, and the haze can be reduced.
  • the linear expansion coefficient (CTE) of the transparent substrate is preferably 20 ppm / K or less.
  • the softening point of the transparent substrate is preferably 300 ° C. or higher.
  • the film forming temperature of the transparent conductive thin film becomes a high temperature of 200 ° C. or higher. This is to make a transparent substrate that can withstand such high temperatures.
  • the linear expansion coefficient (CTE) and softening point of the transparent substrate can be measured by using a Shimadzu TMA-50 and raising the temperature at a rate of temperature increase of 5 ° C./min.
  • the transparent substrate of the present invention has high transparency, heat resistance, and good flexibility as described above. Therefore, the transparent substrate of the present invention is an optical material such as a flat panel display such as a liquid crystal display element and an organic EL display element or a transparent substrate of a flexible display (image display device), a touch panel, a solar cell substrate, an optical lens, and an optical element. Suitable for Especially, the transparent substrate of this invention is suitable for the transparent substrate of a flat panel display or a flexible display (image display apparatus). Below, the example of the liquid crystal display device which comprises the transparent substrate of this invention as a glass substrate of a liquid crystal cell is demonstrated.
  • the liquid crystal display device includes (A) a surface light source for a liquid crystal backlight, (B) at least one or more optical elements, and (C) a liquid crystal panel in which a liquid crystal cell is sandwiched between two or more polarizing plates.
  • the members (A) to (C) are preferably arranged in the order of (A), (B), and (C).
  • the surface light source for liquid crystal backlight is a sidelight (edge light) type surface light source in which a known light source is disposed on the side of the light guide plate, or a known light source is arranged under the diffusion plate. It can be a direct type surface light source. Examples of known light sources include cold cathode fluorescent lamps (CCFL), hot cathode fluorescent lamps (HCFL), external electrode fluorescent lamps (EEFL), flat fluorescent lamps (FFL), light emitting diode elements (LEDs), organic electroluminescent elements (OLEDs). ) Is included.
  • CCFL cold cathode fluorescent lamps
  • HCFL hot cathode fluorescent lamps
  • EEFL external electrode fluorescent lamps
  • FTL flat fluorescent lamps
  • LEDs light emitting diode elements
  • OLEDs organic electroluminescent elements
  • optical element is an element which diffuses the light from the surface light source for liquid crystal backlights.
  • optical element include a diffusion film coated with a filler or a bead-containing binder, a prism sheet, and a microlens sheet.
  • a liquid crystal panel in which a liquid crystal cell is sandwiched between two or more polarizing plates A liquid crystal panel has a liquid crystal cell and two or more polarizing plates that sandwich the liquid crystal cell.
  • the liquid crystal cell includes a liquid crystal sealed between two transparent substrates. This transparent substrate can be used as the transparent substrate of the present invention. Matrix TFTs, color filters, and the like are disposed on the surface of the transparent substrate of the liquid crystal cell.
  • the polarizing plate may also be made of a known material, and examples thereof include a dichroic polarizing plate using a dichroic dye.
  • the transparent substrate of the present invention has high transparency and heat resistance. For this reason, when the transparent substrate of this invention is made into the glass substrate of a liquid crystal cell, for example, generation
  • the transparent polyimide composition of this invention may be one aspect
  • X in the general formula (1) is the same as X in the general formula (11); and Y in the general formula (2) is the same as X in the general formula (12).
  • the polyimide copolymer may be a random copolymer including the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may be a block copolymer. .
  • the total of the number of structural units represented by the general formula (1) and the number of structural units represented by the general formula (2) is 50% or more with respect to the total number of structural units in the polyimide copolymer. Preferably, it is 80% or more.
  • the polyimide containing the structural unit represented by the general formula (1) as a main component in the mixture of polyimides may be a polyimide substantially composed of the structural unit represented by the general formula (1). Ingredients may be included.
  • the polyimide containing the structural unit represented by the general formula (2) as a main component may be a polyimide qualitatively composed of the structural unit represented by the general formula (2), and may contain a small amount of a copolymer component. .
  • Both the polyimide composed of the structural unit represented by the general formula (1) and the polyimide composed of the structural unit represented by the general formula (2) have a group derived from norbornanediamine. Therefore, any polyimide has high transparency with respect to visible light. Furthermore, the polyimide composed of the structural unit represented by the general formula (1) has a high refractive index of 1.59 to 1.65 at a wavelength of 589 nm; the polyimide composed of the structural unit represented by the general formula (2) Has a low refractive index of 1.52 to 1.55 at a wavelength of 589 nm.
  • the transparent polyimide composition of the present invention is a copolymerized polyimide in which the copolymerization ratio of a structural unit that gives a transparent polyimide with a high refractive index at a wavelength of 589 nm and a structural unit that gives a transparent polyimide with a low refractive index is adjusted.
  • a mixing ratio of a transparent polyimide having a high refractive index and a transparent polyimide having a low refractive index at a wavelength of 589 nm (a polyimide containing as a main component a structural unit represented by the formula (1) and a formula (2)
  • the polyimide mixture which adjusted the mixing ratio with the polyimide which contains the structural unit represented as a main component is included.
  • the molar ratio of the structural unit represented by Formula (1) and the structural unit represented by Formula (2) is adjusted, and the refractive index of a transparent polyimide composition is controlled precisely.
  • the copolymerization ratio (molar ratio) (1) :( 2) of the structural unit represented by the formula (1) and the structural unit represented by the formula (2), or a mixture of polyimides is not particularly limited. For example, it can be set to 5:95 to 30:70.
  • a polyimide containing a divalent organic group derived from an aliphatic diamine such as norbornane diamine has higher transparency than an aromatic diamine.
  • polyimides derived from alicyclic hydrocarbon diamines have low crystallinity and are therefore easily formed into films.
  • a polyimide containing a divalent organic group derived from norbornanediamine has high transparency and an appropriate glass transition temperature, and is more easily formed into a film. For this reason, the structural unit represented by General formula (1) and General formula (2) contains the bivalent group induced
  • norbornanediamine examples include 2,3-diaminomethyl-bicyclo [2.2.1] heptane, 2,5-diaminomethyl-bicyclo [2.2.1] heptane, 2,6-diaminomethyl-bicyclo [ 2.2.1] heptane, 2,7-diaminomethyl-bicyclo [2.2.1] heptane and the like; preferably 2,5-diaminomethyl-bicyclo [2.2.1] heptane, 2, 6-diaminomethyl-bicyclo [2.2.1] heptane.
  • Each norbornane diamine includes stereoisomers.
  • the divalent groups derived from a plurality of norbornanediamines may be the same or different.
  • the refractive index of the transparent polyimide composition of the present invention is adjusted according to the refractive index of the combined inorganic filler (reinforcing material).
  • the standard of adjustment is the same as that of the transparent polyimide in the base material (I) of the transparent substrate.
  • the refractive index of the transparent polyimide composition can be adjusted by the type of combination of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the copolymerization ratio, or the mixing ratio.
  • the specific method for increasing the refractive index of the transparent polyimide composition and the specific method for decreasing the refractive index of the transparent polyimide composition are the same as those for the transparent polyimide in the base material (I) of the transparent substrate.
  • Examples of preferred combinations of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) include the structural unit represented by the formula (1a) and the formula (2a).
  • the combination with the structural unit represented, the combination with the structural unit represented by Formula (1a), and the structural unit represented by Formula (2b), etc. are contained.
  • the polyimide mixture containing the structural unit represented can control the refractive index, has high heat resistance, and has a low coefficient of linear expansion.
  • a polyimide copolymer containing a structural unit represented by the formula (1a) and a structural unit represented by the formula (2b), or a polyimide containing a structural unit represented by the formula (1a) and the formula (2b) In addition to being able to control the refractive index, the polyimide mixture containing the structural unit represented by) has high transparency.
  • the copolymerization ratio (molar ratio) between the structural unit represented by the formula (1a) and the structural unit represented by the formula (2a) (1a): (2a), or a mixture of polyimides or a mixture of polyimides
  • the mixing ratio (molar ratio) (1a) :( 2a) of the polyimide containing the structural unit represented by the formula (1a) and the polyimide containing the structural unit represented by the formula (2a) is preferably 5:95 to 30:70.
  • Mating ratio (molar ratio) (1a) :( 2a) of a polyimide containing a structural unit represented by the formula (1a) and a polyimide containing a structural unit represented by the formula (2a) in a polyimide mixture Means the ratio of the number of structural units represented by the formula (1a) and the number of structural units represented by the formula (2a) of the polyimide contained in the mixture.
  • the mixing ratio (molar ratio) of the polyimide containing the structural unit represented by the formula (1a) and the polyimide containing the structural unit represented by the formula (2b) (1a) :( 2b) also refers to the ratio of the number of structural units represented by formula (1a) to the number of structural units represented by formula (2a) of the polyimide contained in the mixture.
  • the polyimide copolymer may further include other structural units other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
  • the polyimide mixture further includes a polyimide containing a structural unit represented by general formula (1) as a main component and another polyimide other than a polyimide containing a structural unit represented by general formula (2) as a main component. May be included.
  • the transparent polyimide composition of the present invention may contain an inorganic filler.
  • an inorganic filler By including an inorganic filler, the mechanical strength of the transparent polyimide composition can be increased, or the linear expansion coefficient can be decreased.
  • the inorganic filler may be fibrous or powdery. The average particle diameter of the powdery inorganic filler is, for example, 2 ⁇ m or less.
  • Examples of the inorganic filler and preferred contents are the same as those of the inorganic filler contained in the base material (I) of the transparent substrate.
  • the transparent polyimide composition of the present invention is a thermoplastic resin or thermosetting resin other than a polyimide copolymer or a mixture of polyimides, various additives, etc., as long as the transparency and refractive index controllability are not impaired. May further be included.
  • various additives include a surface treatment agent (for example, a silane coupling agent) for facilitating the familiarization of the glass filler and the transparent polyimide composition.
  • the glass transition temperature of the transparent polyimide composition is preferably 180 ° C to 300 ° C. This is because the transparent polyimide composition is imparted with a certain level of high heat resistance. Moreover, although the decomposition temperature of a polyimide may exceed 300 degreeC, it is preferable to have a glass transition temperature below a decomposition temperature.
  • the glass transition temperature of the transparent polyimide composition can be measured at a rate of temperature increase of 5 ° C./min using Shimadzu Corporation TGA-50.
  • the transparent polyimide composition of the present invention has high transparency and allows precise control of the refractive index. Moreover, the transparent polyimide composition of the present invention has good flexibility. For this reason, a transparent polyimide composition is suitable for optical materials, such as a transparent substrate of a flat panel display or a flexible display, such as a liquid crystal display element and an organic EL display element, a touch panel, and a solar cell substrate.
  • the transparent polyimide composition of the present invention has high transparency and can precisely control the refractive index while maintaining the inherent heat resistance of polyimide. For this reason, it is easy to control the difference in refractive index with various inorganic fillers, and a transparent substrate having high transparency and heat resistance can be provided.
  • Polyamic acid composition The transparent polyimide composition of the present invention is obtained by imidizing a polyamic acid composition.
  • the polyamic acid composition of the present invention is represented by a polyamic acid copolymer containing a structural unit represented by the general formula (3) and a structural unit represented by the general formula (4), or represented by the general formula (3). And a polyamic acid containing a structural unit represented by the general formula (4).
  • X in the general formula (3) is defined in the same manner as X in the general formula (1).
  • Y in general formula (4) is defined similarly to Y in general formula (2).
  • the mixing ratio (molar ratio) of the polyimide containing the structural unit represented by formula (4) and the polyimide containing the structural unit represented by the general formula (4) is the same as the copolymerization ratio or mixing ratio in the transparent polyimide composition described above. It is.
  • the total amount of the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) in the polyamic acid copolymer, and the general formula (3) in the polyamic acid mixture is the same as that of the transparent polyimide composition described above.
  • the polyamic acid copolymer can be obtained by any method.
  • a block copolymer may be obtained by reacting an amic acid oligomer containing a structural unit represented by the general formula (3) with an amic acid oligomer containing a structural unit represented by the general formula (4); Norbornanediamine contained in the structural unit represented by the general formulas (3) and (4), acid dianhydride contained in the structural unit represented by the general formula (3), and represented by the general formula (4)
  • a random copolymer may be obtained by mixing and reacting an acid dianhydride contained in the structural unit. You may perform reaction in a solvent as needed.
  • the reaction solvent is not particularly limited as long as it can dissolve the polyamic acid.
  • solvents include phenolic solvents such as phenol, chlorophenol, cresol, xylenol; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-
  • phenolic solvents such as phenol, chlorophenol, cresol, xylenol
  • aprotic amide solvents such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, and hexamethylphosphorotriamide.
  • the E-type mechanical viscosity at 25 ° C. of the polyamic acid composition is preferably 300 mPa ⁇ s to 15000 mPa ⁇ s, and more preferably 300 mPa ⁇ s to 1000 mPa ⁇ s. If E type mechanical viscosity is the said range, it will be excellent in the impregnation property to a glass cloth etc.
  • the E-type mechanical viscosity can be measured using a rotor No. 4 with an E-type measuring instrument (TVH-22H) manufactured by Toki Sangyo Co., Ltd.
  • BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 6FDA: 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,1,3,3,3-hexafluoro Propane dianhydride
  • H-BPDA 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride
  • NBDA norbornanediamine
  • DMAc N, N-dimethylacetamide
  • Example 1 Synthesis of Polyamic Acid Copolymer 0.028 mol BPDA, 0.172 mol 6FDA (BPDA: 6FDA molar ratio 14:86), and 174 g in a vessel equipped with a stirrer, nitrogen inlet tube, and thermometer Of DMAc was added and stirred under ice-cooling under a nitrogen stream. To this solution, a mixture of 30.85 g (0.2 mol) of NBDA and 95.50 g of DMAc was gradually added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 12 hours while cooling with water to obtain a polyamic acid copolymer. The obtained polyamic acid copolymer contains a structural unit obtained by reacting NBDA and BPDA and a structural unit obtained by reacting NBDA and 6FDA.
  • Example 2 Instead of 0.028 mol BPDA and 0.172 mol 6FDA in Example 1, 0.024 mol BPDA and 0.176 mol H-BPDA (with a BPDA: H-BPDA molar ratio of 12:88 ) was used in the same manner as in Example 1 to prepare a polyamic acid copolymer solution.
  • the obtained polyamic acid copolymer contains a structural unit obtained by reacting NBDA and BPDA and a structural unit obtained by reacting NBDA and H-BPDA.
  • Example 3 Instead of 0.028 mol BPDA and 0.172 mol 6FDA in Example 1, 0.07 mol BPDA and 0.13 mol 6FDA (BPDA: 6FDA molar ratio was 35:65) were used. Except for the above, a polyamic acid copolymer solution was prepared in the same manner as in Example 1. The obtained polyamic acid copolymer contains a structural unit obtained by reacting NBDA and BPDA and a structural unit obtained by reacting NBDA and 6FDA.
  • Example 4 instead of 0.028 mol BPDA and 0.172 mol 6FDA in Example 1, 0.07 mol BPDA, 0.13 mol H-BPDA and (BPDA: H-BPDA molar ratio is 35: A polyamic acid copolymer solution was prepared in the same manner as in Example 1 except that 65) was used. The obtained polyamic acid copolymer contains a structural unit obtained by reacting NBDA and BPDA and a structural unit obtained by reacting NBDA and H-BPDA.
  • Example 5 The mixing ratio (molar ratio) of the polyamic acid for polyimide with high refractive index obtained in Production Example 1 and the polyamic acid for polyimide with low refractive index obtained in Production Example 2 was 14:86. A polyamic acid mixture was obtained.
  • Example 6 The mixing ratio (molar ratio) of the polyamic acid for polyimide with high refractive index obtained in Production Example 1 and the polyamic acid for polyimide with low refractive index obtained in Production Example 3 was 12:88. A polyamic acid mixture was obtained.
  • Example 7 The mixing ratio (molar ratio) of the polyamic acid for polyimide with high refractive index obtained in Production Example 1 and the polyamic acid for polyimide with low refractive index obtained in Production Example 2 was mixed so as to be 35:65. Obtained a polyamic acid mixture in the same manner as in Example 5.
  • Example 8 The mixing ratio (molar ratio) of the polyamic acid for polyimide with high refractive index obtained in Production Example 1 and the polyamic acid for polyimide with low refractive index obtained in Production Example 3 was mixed so as to be 35:65. Obtained a polyamic acid mixture in the same manner as in Example 6.
  • E-type mechanical viscosity The E-type mechanical viscosity of the polyamic acid (copolymer) solution at 25 ° C was measured using a rotor No. 4 of an E-type measuring instrument TVH-22H manufactured by Toki Sangyo Co., Ltd.
  • the refractive index at a wavelength of 589 nm of the transparent polyimide film was measured at 23 ° C. with an Abbe refractometer DR-M2 type (manufactured by Atago Co., Ltd.). Further, assuming that a transparent polyimide film and E glass having a refractive index of 1.558 at a wavelength of 589 nm are combined, the difference in refractive index between the transparent polyimide film and E glass was determined.
  • the difference in refractive index between the transparent polyimide film and E glass is preferably 0.010 or less.
  • a polyimide having high transparency can be prepared by preparing a polyimide copolymer or a mixture of polyimides having a small refractive index difference with the inorganic filler according to the kind of the inorganic filler to be blended. It is possible to obtain a composition.
  • Example 9 1) Preparation of base material (I) As an inorganic filler, a glass cloth (manufactured by Nittobo, WEA1035, thickness 30 ⁇ m, E glass, refractive index 1.558) was prepared. This glass cloth was impregnated with the polyamic acid copolymer solution obtained in Example 1, and then the solvent was removed and heated (imidized) at 250 ° C. to obtain a substrate (I )
  • the transparent polyimide film obtained in 2) was laminated on both surfaces of the substrate (I) obtained in 1). This laminate was set in a press machine and heat-pressed at 310 ° C. to be heat-sealed. As a result, a transparent substrate having a thickness of 90 to 100 ⁇ m was obtained.
  • Example 10 instead of the polyamic acid copolymer solution obtained in Example 1, the polyamic acid copolymer solution obtained in Example 2 was used instead of the polyamic acid copolymer solution obtained in Example 1 in the production of the substrate (I) and the transparent polyimide film to be the layer (II).
  • a transparent substrate was produced in the same manner as in Example 9 except that was used.
  • Example 11 instead of the polyamic acid copolymer solution obtained in Example 1, the polyamic acid mixed solution obtained in Example 5 was used in the production of the transparent polyimide film to be the base material (I) and the layer (II). A transparent substrate was produced in the same manner as in Example 9 except that.
  • Example 12 In preparing the transparent polyimide film to be the base material (I) and the layer (II), the polyamic acid mixed solution obtained in Example 6 was used instead of the polyamic acid copolymer solution obtained in Example 1. A transparent substrate was produced in the same manner as in Example 9 except that.
  • Example 13 In Example 9, a transparent substrate was produced in the same manner as in Example 9 except that the thickness per layer of the transparent polyimide film to be the layer (II) was about 60 ⁇ m.
  • the linear expansion coefficient (CTE), softening point, and optical properties (total light transmittance and haze) of the transparent substrates obtained in Examples 9 to 13 and Comparative Examples 1 to 7 were measured by the same method as described above. Furthermore, in the transparent substrates obtained in Examples 9 to 13 and Comparative Examples 1 to 7, the resin content with respect to 100 parts by weight of the glass cloth and the light transmittance in the visible light region were measured by the following methods. These measurement results are shown in Table 3.
  • the transparent substrates of Examples 9 to 12 have a high light transmittance of 87% or more and a low haze of 12% or less, it can be seen that the transparency is high. Further, it is suggested that the transparent substrates of Examples 9 to 12 have a low coefficient of linear expansion (CTE) of 20 ppm / K or less and high heat resistance. It can be seen that the transparent substrate of Example 13 has high light transmittance and low haze despite having the thick layer (II). In contrast, the transparent substrates of Comparative Examples 1 to 7 have low light transmittance and high haze.
  • CTE coefficient of linear expansion
  • the transparent substrate of the present invention has high transparency, heat resistance, and flexibility. Therefore, the transparent substrate of the present invention is an optical material such as a flat panel display such as a liquid crystal display element and an organic EL display element or a transparent substrate of a flexible display (image display device), a touch panel, a solar cell substrate, an optical lens, and an optical element.
  • a flat panel display such as a liquid crystal display element and an organic EL display element
  • a touch panel such as a touch panel, a solar cell substrate, an optical lens, and an optical element.
  • the transparent polyimide composition of the present invention has high transparency and can precisely control the refractive index.
  • a transparent polyimide composition can be preferably utilized for optical materials, such as a transparent substrate of a flat panel display, such as a liquid crystal display element and an organic EL display element, or a flexible display, a touch panel, a solar cell substrate.

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Abstract

L'invention concerne un substrat transparent doté aussi bien de transparence que de résistance thermique. En outre, l'invention concerne une composition de résine polyimide transparente sans couleur ayant un indice de réfraction que l'on peut réguler avec précision sans compromettre la résistance thermique élevée de la résine de polyimide réelle. Un substrat transparent présente un matériau de base (I) comprenant un polyimide thermoplastique transparent et une charge inorganique. Le polyimide thermoplastique transparent comprend des unités structurales a représentées par la formule générale (11) et des unités structurales ß représentées par la formule générale (12). L'indice de réfraction à une longueur d'onde de 589 nm du polyimide formé à partir des unités structurales a représentées par la formule générale (11) est compris entre 1,59 et 1,65, et l'indice de réfraction à une longueur d'onde de 589 nm du polyimide formé à partir des unités structurales ß représentées par la formule générale (12) est comprise entre 1,52 et 1,55.
PCT/JP2010/005551 2009-09-18 2010-09-10 Polyimide thermoplastique transparent et substrat transparent le contenant Ceased WO2011033751A1 (fr)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013164499A (ja) * 2012-02-10 2013-08-22 Canon Inc 光学用部材及びその製造方法
WO2014041816A1 (fr) * 2012-09-14 2014-03-20 三井化学株式会社 Stratifié de polyimide transparent et son procédé de fabrication
KR101387031B1 (ko) 2013-02-28 2014-04-18 한국과학기술원 유리섬유직물이 매립된 플렉시블 디스플레이용 무색투명 폴리이미드 필름 제조방법
WO2014084699A1 (fr) * 2012-11-30 2014-06-05 주식회사 엘지화학 Substrat destiné à un élément électronique organique
KR101482707B1 (ko) * 2013-02-27 2015-01-14 한국과학기술원 디스플레이 기판 및 커버 윈도우용 유리섬유직물이 함침된 무색투명 폴리이미드 필름의 표면 평탄화 방법
JP2015081285A (ja) * 2013-10-22 2015-04-27 日産化学工業株式会社 ディスプレイ基板用樹脂組成物
WO2015163314A1 (fr) * 2014-04-23 2015-10-29 Ｊｘ日鉱日石エネルギー株式会社 Dianhydride tétracarboxylique, acide polyamique, polyimide, leurs procédés de production, et solution d'acide polyamique
JP2016506023A (ja) * 2012-11-30 2016-02-25 エルジー・ケム・リミテッド 有機電子素子用基板
CN105408948A (zh) * 2013-09-30 2016-03-16 株式会社Lg化学 用于有机电子器件的基板
JP2016130325A (ja) * 2016-04-18 2016-07-21 宇部興産株式会社 ポリイミド及びポリイミド前駆体
WO2016129329A1 (fr) * 2015-02-09 2016-08-18 コニカミノルタ株式会社 Procédé de fabrication d'un film stratifié transparent résistant à la chaleur, film stratifié transparent résistant à la chaleur, carte de circuit imprimé souple, substrat pour affichage souple, plaque avant pour affichage souple, dispositif d'éclairage à led, et dispositif d'affichage électroluminescent organique
WO2017030019A1 (fr) * 2015-08-14 2017-02-23 Ｊｘエネルギー株式会社 Dianhydride tétracarboxylique, composé carbonyle, acide polyamique et polyimide, et procédés respectifs de production de ces composés, solution préparée à l'aide d'acide polyamique, et film produit en utilisant un polyimide
JP2017144371A (ja) * 2016-02-16 2017-08-24 平岡織染株式会社 高温耐熱性シートの製造方法
WO2017191830A1 (fr) * 2016-05-02 2017-11-09 三菱瓦斯化学株式会社 Résine polyimide, composition de résine polyimide, et pellicule polyimide
US9896600B2 (en) * 2014-07-29 2018-02-20 Boe Technology Group Co., Ltd. Functional material and method for preparing the same, touch structure and touch display device
JP2018095715A (ja) * 2016-12-12 2018-06-21 コニカミノルタ株式会社 ポリイミドフィルムおよび当該フィルムを用いる表示装置
KR20200077453A (ko) * 2018-12-20 2020-06-30 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름
JP2021059731A (ja) * 2017-09-29 2021-04-15 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム
KR20210112514A (ko) * 2020-03-05 2021-09-15 에스케이씨 주식회사 고분자 필름, 이를 포함하는 전면판 및 디스플레이 장치
KR20240011148A (ko) 2021-05-21 2024-01-25 혼슈우 카가쿠고교 가부시키가이샤 무색 투명 가공품용 폴리이미드 수지 재료, 신규한 폴리이미드

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0756030A (ja) * 1993-08-19 1995-03-03 Fujitsu Ltd プラスチック光導波路
WO1998029471A1 (fr) * 1996-12-27 1998-07-09 Maruzen Petrochemical Co., Ltd. Resine polyimide soluble, son procede de preparation, et composition de solution de resine polyimide
WO2000068318A1 (fr) * 1999-05-10 2000-11-16 Teijin Limited Composition de resine contenant un polyimide cristallin
WO2002010253A1 (fr) * 2000-07-27 2002-02-07 Mitsui Chemicals, Inc. Acide polyamique, polyimide, leur procede de production, et film de polyimide
JP2003287634A (ja) * 2002-01-22 2003-10-10 Sumitomo Bakelite Co Ltd プラスチック光導波路用材料及び光導波路
JP2003313294A (ja) * 2002-04-26 2003-11-06 Central Glass Co Ltd フッ素化ポリイミドを用いた光部品
JP2004149711A (ja) * 2002-10-31 2004-05-27 Toshiba Corp ポリイミド光学材料、ポリイミド前駆体溶液、および光導波路素子
JP2005349726A (ja) * 2004-06-11 2005-12-22 Toray Ind Inc 二軸配向フィルム
JP2006176586A (ja) * 2004-12-21 2006-07-06 Sumitomo Bakelite Co Ltd 透明複合体組成物及び光学シート並びに表示素子用プラスチック基板
WO2008010483A1 (fr) * 2006-07-21 2008-01-24 Toray Industries, Inc. Composition de résine pour film mince retard, substrat de filtre coloré pour un dispositif d'affichage à cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de fabrication d'un substrat de filtre coloré pour un dispositif d'affichage à cristaux liquides ayant un film
JP2008308629A (ja) * 2007-06-18 2008-12-25 Nippon Electric Glass Co Ltd 樹脂組成物
WO2009069688A1 (fr) * 2007-11-30 2009-06-04 Mitsui Chemicals, Inc. Matière composite de polyimide et son film
WO2010055899A1 (fr) * 2008-11-14 2010-05-20 日清紡ホールディングス株式会社 Composition de résine, corps formé de résine transparente et film de revêtement l'utilisant

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0756030A (ja) * 1993-08-19 1995-03-03 Fujitsu Ltd プラスチック光導波路
WO1998029471A1 (fr) * 1996-12-27 1998-07-09 Maruzen Petrochemical Co., Ltd. Resine polyimide soluble, son procede de preparation, et composition de solution de resine polyimide
WO2000068318A1 (fr) * 1999-05-10 2000-11-16 Teijin Limited Composition de resine contenant un polyimide cristallin
WO2002010253A1 (fr) * 2000-07-27 2002-02-07 Mitsui Chemicals, Inc. Acide polyamique, polyimide, leur procede de production, et film de polyimide
JP2003287634A (ja) * 2002-01-22 2003-10-10 Sumitomo Bakelite Co Ltd プラスチック光導波路用材料及び光導波路
JP2003313294A (ja) * 2002-04-26 2003-11-06 Central Glass Co Ltd フッ素化ポリイミドを用いた光部品
JP2004149711A (ja) * 2002-10-31 2004-05-27 Toshiba Corp ポリイミド光学材料、ポリイミド前駆体溶液、および光導波路素子
JP2005349726A (ja) * 2004-06-11 2005-12-22 Toray Ind Inc 二軸配向フィルム
JP2006176586A (ja) * 2004-12-21 2006-07-06 Sumitomo Bakelite Co Ltd 透明複合体組成物及び光学シート並びに表示素子用プラスチック基板
WO2008010483A1 (fr) * 2006-07-21 2008-01-24 Toray Industries, Inc. Composition de résine pour film mince retard, substrat de filtre coloré pour un dispositif d'affichage à cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de fabrication d'un substrat de filtre coloré pour un dispositif d'affichage à cristaux liquides ayant un film
JP2008308629A (ja) * 2007-06-18 2008-12-25 Nippon Electric Glass Co Ltd 樹脂組成物
WO2009069688A1 (fr) * 2007-11-30 2009-06-04 Mitsui Chemicals, Inc. Matière composite de polyimide et son film
WO2010055899A1 (fr) * 2008-11-14 2010-05-20 日清紡ホールディングス株式会社 Composition de résine, corps formé de résine transparente et film de revêtement l'utilisant

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JP2013164499A (ja) * 2012-02-10 2013-08-22 Canon Inc 光学用部材及びその製造方法
WO2014041816A1 (fr) * 2012-09-14 2014-03-20 三井化学株式会社 Stratifié de polyimide transparent et son procédé de fabrication
CN104582960A (zh) * 2012-09-14 2015-04-29 三井化学株式会社 透明聚酰亚胺叠层体及其制造方法
CN104582960B (zh) * 2012-09-14 2017-03-08 三井化学株式会社 透明聚酰亚胺叠层体及其制造方法
WO2014084699A1 (fr) * 2012-11-30 2014-06-05 주식회사 엘지화학 Substrat destiné à un élément électronique organique
US9595684B2 (en) 2012-11-30 2017-03-14 Lg Chem, Ltd. Substrate for organic electronic device having high refractive layer on light scattering, optical functional layer
JP2016506023A (ja) * 2012-11-30 2016-02-25 エルジー・ケム・リミテッド 有機電子素子用基板
JP2016506022A (ja) * 2012-11-30 2016-02-25 エルジー・ケム・リミテッド 有機電子素子用基板
KR101482707B1 (ko) * 2013-02-27 2015-01-14 한국과학기술원 디스플레이 기판 및 커버 윈도우용 유리섬유직물이 함침된 무색투명 폴리이미드 필름의 표면 평탄화 방법
US9469735B2 (en) 2013-02-27 2016-10-18 Korea Advanced Institute Of Science And Technology Method of manufacturing colorless transparent polyimide film having impregnated glass fabric and of flattening surface thereof
US9417472B2 (en) 2013-02-28 2016-08-16 Korea Advanced Institute Of Science And Technology Method for manufacturing colorless transparent glass-fabric reinforced polyimide film for flexible displays
KR101387031B1 (ko) 2013-02-28 2014-04-18 한국과학기술원 유리섬유직물이 매립된 플렉시블 디스플레이용 무색투명 폴리이미드 필름 제조방법
EP3016087B1 (fr) * 2013-09-30 2021-03-31 LG Display Co., Ltd. Substrat pour dispositif électronique organique
CN105408948A (zh) * 2013-09-30 2016-03-16 株式会社Lg化学 用于有机电子器件的基板
JP2016533005A (ja) * 2013-09-30 2016-10-20 エルジー ディスプレイ カンパニー リミテッド 有機電子素子用基板
US10090473B2 (en) 2013-09-30 2018-10-02 Lg Display Co., Ltd. Substrate for organic electronic device
CN105408948B (zh) * 2013-09-30 2018-09-18 乐金显示有限公司 用于有机电子器件的基板
KR101928598B1 (ko) * 2013-09-30 2018-12-12 주식회사 엘지화학 폴리이미드 필름 및 그 제조방법
JP2015081285A (ja) * 2013-10-22 2015-04-27 日産化学工業株式会社 ディスプレイ基板用樹脂組成物
US10513582B2 (en) 2014-04-23 2019-12-24 Jxtg Nippon Oil & Energy Corporation Tetracarboxylic dianhydride, polyamic acid, polyimide, methods for producing the same, and polyamic acid solution
WO2015163314A1 (fr) * 2014-04-23 2015-10-29 Ｊｘ日鉱日石エネルギー株式会社 Dianhydride tétracarboxylique, acide polyamique, polyimide, leurs procédés de production, et solution d'acide polyamique
JPWO2015163314A1 (ja) * 2014-04-23 2017-04-20 Ｊｘエネルギー株式会社 テトラカルボン酸二無水物、ポリアミド酸、ポリイミド、及び、それらの製造方法、並びに、ポリアミド酸溶液
US9896600B2 (en) * 2014-07-29 2018-02-20 Boe Technology Group Co., Ltd. Functional material and method for preparing the same, touch structure and touch display device
WO2016129329A1 (fr) * 2015-02-09 2016-08-18 コニカミノルタ株式会社 Procédé de fabrication d'un film stratifié transparent résistant à la chaleur, film stratifié transparent résistant à la chaleur, carte de circuit imprimé souple, substrat pour affichage souple, plaque avant pour affichage souple, dispositif d'éclairage à led, et dispositif d'affichage électroluminescent organique
CN107922367A (zh) * 2015-08-14 2018-04-17 Jxtg能源株式会社 四羧酸二酐、羰基化合物、聚酰胺酸、聚酰亚胺及它们的制造方法、使用聚酰胺酸的溶液以及使用聚酰亚胺的薄膜
JPWO2017030019A1 (ja) * 2015-08-14 2018-05-31 Ｊｘｔｇエネルギー株式会社 テトラカルボン酸二無水物、カルボニル化合物、ポリアミド酸、ポリイミド及びそれらの製造方法、ポリアミド酸を用いた溶液、並びに、ポリイミドを用いたフィルム
WO2017030019A1 (fr) * 2015-08-14 2017-02-23 Ｊｘエネルギー株式会社 Dianhydride tétracarboxylique, composé carbonyle, acide polyamique et polyimide, et procédés respectifs de production de ces composés, solution préparée à l'aide d'acide polyamique, et film produit en utilisant un polyimide
JP2017144371A (ja) * 2016-02-16 2017-08-24 平岡織染株式会社 高温耐熱性シートの製造方法
JP2016130325A (ja) * 2016-04-18 2016-07-21 宇部興産株式会社 ポリイミド及びポリイミド前駆体
JP7003914B2 (ja) 2016-05-02 2022-02-10 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミド樹脂組成物、及びポリイミドフィルム
KR20190003545A (ko) * 2016-05-02 2019-01-09 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리이미드 수지, 폴리이미드 수지 조성물, 및 폴리이미드 필름
JPWO2017191830A1 (ja) * 2016-05-02 2019-03-07 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミド樹脂組成物、及びポリイミドフィルム
KR102363084B1 (ko) * 2016-05-02 2022-02-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리이미드 수지, 폴리이미드 수지 조성물, 및 폴리이미드 필름
WO2017191830A1 (fr) * 2016-05-02 2017-11-09 三菱瓦斯化学株式会社 Résine polyimide, composition de résine polyimide, et pellicule polyimide
US11332578B2 (en) 2016-05-02 2022-05-17 Mitsubishi Gas Chemical Company, Inc. Polyimide resin, polyimide resin composition, and polyimide film
CN109071811B (zh) * 2016-05-02 2021-06-25 三菱瓦斯化学株式会社 聚酰亚胺树脂、聚酰亚胺树脂组合物和聚酰亚胺薄膜
CN109071811A (zh) * 2016-05-02 2018-12-21 三菱瓦斯化学株式会社 聚酰亚胺树脂、聚酰亚胺树脂组合物和聚酰亚胺薄膜
JP2018095715A (ja) * 2016-12-12 2018-06-21 コニカミノルタ株式会社 ポリイミドフィルムおよび当該フィルムを用いる表示装置
JP2021059731A (ja) * 2017-09-29 2021-04-15 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム
JP6996609B2 (ja) 2017-09-29 2022-01-17 三菱瓦斯化学株式会社 ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム
KR20200077453A (ko) * 2018-12-20 2020-06-30 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름
KR102452136B1 (ko) 2018-12-20 2022-10-07 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름
KR20210112514A (ko) * 2020-03-05 2021-09-15 에스케이씨 주식회사 고분자 필름, 이를 포함하는 전면판 및 디스플레이 장치
KR102369352B1 (ko) * 2020-03-05 2022-03-02 에스케이씨 주식회사 고분자 필름, 이를 포함하는 전면판 및 디스플레이 장치
KR20240011148A (ko) 2021-05-21 2024-01-25 혼슈우 카가쿠고교 가부시키가이샤 무색 투명 가공품용 폴리이미드 수지 재료, 신규한 폴리이미드

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