WO2017057741A1 - Composition pour la formation d'un film fin en résine - Google Patents

Composition pour la formation d'un film fin en résine Download PDF

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Publication number
WO2017057741A1
WO2017057741A1 PCT/JP2016/079145 JP2016079145W WO2017057741A1 WO 2017057741 A1 WO2017057741 A1 WO 2017057741A1 JP 2016079145 W JP2016079145 W JP 2016079145W WO 2017057741 A1 WO2017057741 A1 WO 2017057741A1
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Prior art keywords
thin film
resin thin
composition
group
polyimide
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PCT/JP2016/079145
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English (en)
Japanese (ja)
Inventor
江原　和也
鎮嘉 葉
邦慶 何
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日産化学工業株式会社
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Priority to JP2017543651A priority Critical patent/JP6990354B2/ja
Priority to CN201680056917.0A priority patent/CN108137924B/zh
Priority to KR1020187010600A priority patent/KR102599925B1/ko
Publication of WO2017057741A1 publication Critical patent/WO2017057741A1/fr

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    • 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
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a composition for forming a resin thin film, and more specifically to a composition for forming a resin thin film suitable for use in a display substrate such as a flexible display substrate.
  • JP-A-60-188427 JP 58-208322 A Japanese Patent Laying-Open No. 2015-63655 International Publication 2011/149018 Pamphlet US Patent Application Publication No. 2011/130495 International Publication 2012/129422 Pamphlet
  • the resin material when a polyimide resin material is used as a display substrate, it is desirable and required that the resin material not only has excellent transparency and flexibility, but also has a low retardation as one of the required performances.
  • the retardation phase difference
  • the retardation means the product of birefringence (difference between two orthogonal refractive indexes) and the film thickness. This numerical value, particularly the retardation in the thickness direction, is important because it affects the viewing angle characteristics. It is a numerical value. It is known that a large retardation value can cause a deterioration in display quality of a display (see, for example, Patent Document 4).
  • the present invention has been made in view of such circumstances, and has not only excellent heat resistance and flexibility, but also has a feature of low retardation, and further excellent transparency and solvent resistance.
  • Another object of the present invention is to provide a resin thin film forming composition that provides a resin thin film that is suitable as a base film for a display substrate, and particularly has excellent performance as a base film for a flexible display substrate.
  • Patent Documents 5 and 6 disclose compositions containing a crosslinking agent. However, none of the documents includes a description that teaches the configuration of the present invention or a specific effect produced thereby, or a description that suggests them.
  • the present invention provides the first aspect as follows: Polyimide, Silicon dioxide particles having an average particle size of 100 nm or less calculated from a specific surface area value measured by a nitrogen adsorption method, A compound composed only of a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom, having two or more groups selected from the group consisting of a hydroxy group, an epoxy group and an alkoxy group having 1 to 5 carbon atoms, and The present invention also relates to a composition for forming a resin thin film comprising a crosslinking agent comprising a compound having a cyclic structure, and an organic solvent.
  • the polyimide imidizes a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a diamine component containing a fluorine-containing aromatic diamine. It is related with the composition for resin thin film formation as described in a 1st viewpoint which is a polyimide obtained. As a 3rd viewpoint, the said alicyclic tetracarboxylic dianhydride is related with the composition for resin thin film formation as described in a 2nd viewpoint containing the tetracarboxylic dianhydride represented by Formula (C1).
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
  • a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.
  • the said fluorine-containing aromatic diamine is related with the composition for resin thin film formation as described in a 2nd viewpoint or a 3rd viewpoint containing the diamine represented by a formula (A1).
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)).
  • the present invention relates to the composition for forming a resin thin film according to any one of the first aspect to the fourth aspect, wherein the mass ratio of the polyimide and the silicon dioxide particles is 7: 3 to 3: 7. .
  • the present invention relates to the resin thin film forming composition according to any one of the first aspect to the fifth aspect, in which an average particle diameter of the silicon dioxide particles is 60 nm or less.
  • a 7th viewpoint it is related with the resin thin film formed from the composition for resin thin film formation as described in any one among a 1st viewpoint thru
  • a resin thin film having a low linear expansion coefficient, excellent heat resistance, high transparency and low retardation, and excellent flexibility and solvent resistance is reproducible. Can be well formed.
  • the resin thin film according to the present invention exhibits a low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, and excellent flexibility and solvent resistance. It can be suitably used as a display substrate.
  • Such a resin thin film forming composition and resin thin film according to the present invention are required to have properties such as high flexibility, low linear expansion coefficient, high transparency (high light transmittance, low yellowness), and low retardation. It can sufficiently cope with the progress in the field of wireless device substrates, particularly flexible display substrates.
  • composition for forming a resin thin film of the present invention contains the following specific polyimide, silicon dioxide particles, a crosslinking agent and an organic solvent.
  • the polyimide used in the present invention is preferably a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride with a diamine component containing a fluorine-containing aromatic diamine. It is a polyimide obtained by converting.
  • the alicyclic tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (C1), and the fluorine-containing aromatic diamine is represented by the following formula (A1). It is preferable that the diamine contains.
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12). (In the formula, a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.)
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)). (In the formula, * represents a bond.)
  • B 1 in the formula is represented by the formulas (X-1), (X-4), (X-6), (X-7). It is preferable that it is a compound.
  • B 2 in the formula is preferably a compound represented by the formula (Y-12) or (Y-13).
  • a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the above formula (C1) and a diamine represented by the above formula (A1) is described below.
  • the monomer unit represented by Formula (2) is included.
  • the alicyclic tetracarboxylic dianhydride for example, the tetracarboxylic dianhydride represented by the above formula (C1) is preferably 90 mol% or more, more preferably 95 mol% or more, particularly all Optimally, (100 mol%) is a tetracarboxylic dianhydride represented by the above formula (C1).
  • the fluorine-containing aromatic diamine is preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the diamine represented by the said Formula (A1) may be sufficient as all (100 mol%) of a diamine component.
  • the polyimide used by this invention contains the monomer unit represented by following formula (2).
  • the polyimide of the present invention includes an alicyclic tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the above formula (C1), a diamine component containing a diamine represented by the formula (A1), and In addition to the monomer unit derived from, other monomer units may be included.
  • the content ratio of the other monomer units is arbitrarily determined as long as the properties of the resin thin film formed from the resin thin film forming composition of the present invention are not impaired.
  • the ratio is derived from the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the formula (C1) and the diamine component containing the diamine represented by the formula (A1).
  • the total number of moles of monomer units is preferably less than 20 mol%, more preferably less than 10 mol%, and even more preferably less than 5 mol%.
  • Examples of such other monomer units include, but are not limited to, monomer units having other polyimide structures represented by the formula (3).
  • A represents a tetravalent organic group, preferably a tetravalent group represented by any of the following formulas (A-1) to (A-4).
  • B represents a divalent organic group, preferably a divalent group represented by any one of formulas (B-1) to (B-11).
  • * represents a bond.
  • B represents the above formulas (Y-1) to ( Y-34) may be a divalent group.
  • A represents the above formulas (X-1) to (X It may be a tetravalent group represented by any of -12).
  • a and B may contain only a monomer unit composed of only one of the groups exemplified by the following formula, for example.
  • at least one of A and B may contain two or more monomer units selected from two or more groups exemplified below.
  • each monomer unit is bonded in an arbitrary order.
  • the polyimide used by this invention contains the diamine represented by the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the above-mentioned formula (C1), and a formula (A1).
  • the polyimide containing each monomer unit is represented by the above formula (C1) as a tetracarboxylic dianhydride component.
  • a in the above formula (5) and B in the formula (6) have the same meaning as A and B in the above formula (3), respectively.
  • tetracarboxylic dianhydride represented by the formula (5)
  • tetracarboxylic dianhydrides in which A in the formula (5) is a tetravalent group represented by any one of the above formulas (A-1) to (A-4) are preferable.
  • 4,8-bis (trifluoromethoxy) benzo [1,2-c: 4,5 -C '] difuran-1,3,5,7-tetraone can benzo
  • Examples of the diamine represented by the formula (6) include 2- (trifluoromethyl) benzene-1,4-diamine, 5- (trifluoromethyl) benzene-1,3-diamine, and 5- (trifluoromethyl).
  • aromatic diamines in which B in the formula (6) is a divalent group represented by any one of the formulas (B-1) to (B-11) are preferable, that is, 2,2 ′.
  • -Bis (trifluoromethoxy)-(1,1'-biphenyl) -4,4'-diamine [other name: 2,2'-dimethoxybenzidine], 4,4 '-(perfluoropropane-2,2- Diyl) dianiline, 2,5-bis (trifluoromethyl) benzene-1,4-diamine, 2- (trifluoromethyl) benzene-1,4-diamine, 2-fluorobenzene-1,4-diamine, 4, 4′-oxybis [3- (trifluoromethyl) aniline], 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro [1,1′-biphenyl] -4,4 ′ -
  • the polyimide used in the present invention is represented by the tetracarboxylic dianhydride component including the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and the above formula (A1). It is obtained by imidizing a polyamic acid obtained by reacting a diamine component containing a fluorine-containing aromatic diamine.
  • the reaction from the two components to the polyamic acid is advantageous in that it can proceed relatively easily in an organic solvent and no by-product is formed.
  • the charging ratio (molar ratio) of the diamine component in the reaction between the tetracarboxylic dianhydride component and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid and the polyimide obtained by subsequent imidization.
  • the tetracarboxylic dianhydride component can usually be about 0.8 to 1.2, for example about 0.9 to 1.1, preferably about 0.1. It is about 95 to 1.02. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • the organic solvent used in the reaction between the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the produced polyamic acid dissolves. Specific examples are given below.
  • the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is added here.
  • a method of alternately adding a tetracarboxylic dianhydride component and a diamine compound component may be used.
  • the tetracarboxylic dianhydride component and / or the diamine component are composed of a plurality of types of compounds, they may be reacted in a premixed state, individually individually, or further individually. Low molecular weight substances may be mixed and reacted to form high molecular weight substances.
  • the temperature at the time of synthesizing the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and can be selected, for example, from -20 ° C to 150 ° C. C. to 100.degree. C., usually about 0 to 100.degree. C., preferably about 0 to 70.degree.
  • the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult.
  • the total concentration of the tetracarboxylic dianhydride component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 40% by mass.
  • the initial stage of the reaction can be performed at a high concentration, and then an organic solvent can be added.
  • Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the chemical (catalyst) imidization of polyamic acid is carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution, and igniting the system under a temperature condition of ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. This can be done by stirring.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 1.5 to 20 mol times the amide acid group of the polyamic acid, and the amount of the acid anhydride is 1 to 50 mol of the amide acid group of the polyamic acid. Double, preferably 2 to 30 mole times.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, 1-ethylpiperidine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose. Particularly preferably, it is 50% or more.
  • the filtrate after filtering the reaction solution, the filtrate may be used as it is, or may be diluted or concentrated, and silicon dioxide or the like to be described later may be added thereto to form a resin thin film forming composition.
  • silicon dioxide or the like to be described later may be added thereto to form a resin thin film forming composition.
  • the polyimide used in the present invention has a weight average molecular weight (Mw) in terms of polystyrene of gel permeation chromatography (GPC) in consideration of the strength of the resin thin film, workability when forming the resin thin film, uniformity of the resin thin film, and the like. ) Is preferably 5,000 to 200,000.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, isopropanol, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the organic solvent for dissolving the resin component in the reprecipitation collection step is not particularly limited. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetra Methyl urea, pyridine, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, Examples include diglyme and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvent
  • Silicon dioxide (silica) used in the present invention is not particularly limited, but silicon dioxide in the form of particles, for example, having an average particle diameter of 100 nm or less, for example, 5 nm to 100 nm, preferably 5 nm to 55 nm, can produce a highly transparent thin film. From the viewpoint of well being obtained, the thickness is preferably 5 nm to 50 nm, more preferably 5 nm to 45 nm, still more preferably 5 nm to 35 nm, and further preferably 5 nm to 30 nm.
  • the average particle diameter of silicon dioxide particles is an average particle diameter value calculated from specific surface area values measured by a nitrogen adsorption method using silicon dioxide particles.
  • colloidal silica having the above average particle size can be suitably used, and silica sol can be used as the colloidal silica.
  • silica sol there can be used an aqueous silica sol produced by a known method using a sodium silicate aqueous solution as a raw material, and an organosilica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent.
  • alkoxysilanes such as methyl silicate and ethyl silicate are obtained by hydrolysis and condensation in an organic solvent such as alcohol in the presence of a catalyst (for example, an alkali catalyst such as ammonia, an organic amine compound, or sodium hydroxide).
  • a silica sol obtained by replacing the silica sol with another organic solvent can be used.
  • the present invention preferably uses an organosilica sol whose dispersion medium is an organic solvent.
  • Examples of the organic solvent in the above-described organosilica sol include: lower alcohols such as methyl alcohol, ethyl alcohol and isopropanol; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methyl-2- Examples include cyclic amides such as pyrrolidone; ethers such as ⁇ -butyrolactone; glycols such as ethyl cellosolve and ethylene glycol, acetonitrile, and the like. This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method.
  • the viscosity of the organosilica sol is about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
  • organosilica sols examples include, for example, trade name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.).
  • Product name XBA-ST xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product name EAC-ST ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product Name PMA-ST propylene glycol monomethyl ether acetate dispersed silica sol, Nissan Chemical Industries, Ltd.
  • Trade name MEK-ST methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-UP methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-L examples thereof include, but are not limited to, methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd., and trade name MIBK-ST (methyl isobutyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries
  • the cross-linking agent used in the present invention is a compound composed only of a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom, and is selected from the group consisting of a hydroxy group, an epoxy group and an alkoxy group having 1 to 5 carbon atoms.
  • a cross-linking agent comprising a compound having two or more groups and a ring structure.
  • “consisting only of hydrogen atoms, carbon atoms, nitrogen atoms and oxygen atoms” refers to comprising only atoms selected from the group consisting of the above four atoms, ie, all the above four atoms are included.
  • the crosslinking agent In addition to being composed of only those atoms, it may be composed of only three atoms (for example, hydrogen atom, carbon atom and oxygen atom) of the above four atoms.
  • a crosslinking agent By using such a crosslinking agent, not only can a resin thin film excellent in solvent resistance be obtained with good reproducibility, but also a resin composition with improved storage stability can be realized.
  • the total number of hydroxy groups, epoxy groups and alkoxy groups having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably 3 or more from the viewpoint of realizing the solvent resistance of the resulting resin thin film with good reproducibility. From the viewpoint of realizing the flexibility of the resulting resin thin film with good reproducibility, it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • ring structure possessed by the crosslinking agent include aryl rings such as benzene, nitrogen-containing heteroaryl rings such as pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, cyclopentane, cyclohexane, cycloheptane, etc.
  • cyclic amines such as cycloalkane ring, piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine, hexahydro-1,3,5-triazine and the like.
  • the number of ring structures per compound in the crosslinking agent is not particularly limited as long as it is 1 or more. However, from the viewpoint of obtaining a resin thin film having high flatness by ensuring the solubility of the crosslinking agent in a solvent, 1 or 2 is preferable.
  • the ring structures may be condensed with each other, and an alkane having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a triethylene group, or a propane-2,2-diyl group.
  • the ring structures may be bonded to each other through a linking group such as a diyl group.
  • the molecular weight of the crosslinking agent is not particularly limited as long as it has crosslinking ability and dissolves in the solvent to be used, but the solvent resistance of the resulting resin thin film, the solubility of the crosslinking agent itself in an organic solvent, and easy availability In consideration of properties, price, etc., it is preferably about 100 to 500, more preferably about 150 to 400.
  • the crosslinking agent may further have a group that can be derived from a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom, such as a ketone group or an ester group (bond).
  • Preferred examples of the crosslinking agent include compounds represented by the following formulas (K1) to (K5), and one preferred embodiment of the formula (K4) is a compound represented by the formula (K4-1).
  • a compound represented by the formula (5-1) can be exemplified.
  • each of A 1 and A 2 independently represents an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a triethylene group, or a propane-2,2-diyl group.
  • a 1 is preferably a methylene group or an ethylene group, more preferably a methylene group
  • a 2 is preferably a methylene group or a propane-2,2-diyl group.
  • Each X is independently of each other hydroxy group, epoxy group (oxa-cyclopropyl group), methoxy group, ethoxy group, 1-propyloxy group, isopropyloxy group, 1-butyloxy group, t-butyloxy group, etc.
  • An alkoxy group having 1 to 5 carbon atoms is represented.
  • X is preferably an epoxy group in the formulas (K1) and (K5), and has 1 to 5 carbon atoms in the formulas (K2) and (K3) in consideration of the availability, price, etc. of the crosslinking agent.
  • An alkoxy group is preferable, and a hydroxy group is preferable in the formula (K4).
  • each n is bonded to the benzene ring - (A 1 -X) indicates the number of groups, is an integer of 1 to 5 independently of one another, preferably 2 to 3, more preferably 3.
  • each A 1 is preferably the same group, and each X is preferably the same group.
  • the compounds represented by the above formulas (K1) to (K5) are skeleton compounds such as aryl compounds, heteroaryl compounds, and cyclic amines having the same ring structure as the ring structure in these compounds, epoxy alkyl halide compounds, It can be obtained by reacting an alkoxy halide compound or the like with a carbon-carbon coupling reaction or an N-alkylation reaction, or hydrolyzing the resulting alkoxy moiety.
  • a commercial item may be used for a crosslinking agent, and what was synthesize
  • combining method may be used for it.
  • Commercially available products include CYMEL (registered trademark) 300, 301, 303LF, 303ULF, 304, 350, 3745, XW3106, MM-100, 323, 325, 327, 328, Same 385, Same 370, Same 373, Same 380, Same 1116, Same 1130, Same 1133, Same 1141, Same 1161, Same 1168, Same 3020, Same 202, Same 203, Same 1156, Same MB-94, Same MB- 96, MB-98, 247-10, 651, 658, 683, 683, 688, 1158, MB-14, MI-12-I, MI-97-IX, U-65 UM-15, U-80, U-21-511, U-21-510, U-216-8, U-227-8, U-1050-10, U-1052 -8, the same
  • TEPIC registered trademark
  • V, S, HP, etc. L, PAS, VL, UC manufactured by Nissan Chemical Industries, Ltd.
  • TM-BIP-A manufactured by Asahi Organic Materials Co., Ltd.
  • 1,3,4,6-tetrakis (methoxymethyl) ) Glycoluril hereinafter abbreviated as TMG) (Tokyo Chemical Industry Co., Ltd.) Ltd.), 4,4'-methylenebis (N, N-diglycidyl aniline) (Aldrich Co., Ltd.).
  • the blending ratio of the crosslinking agent is 0.1 to 200% by mass, preferably 0.2 to 100% by mass with respect to the total mass of the polyimide and the silicon dioxide.
  • the resin thin film forming composition of the present invention contains an organic solvent in addition to the polyimide and silicon dioxide.
  • This organic solvent is not specifically limited, For example, the thing similar to the specific example of the reaction solvent used at the time of preparation of the said polyamic acid and a polyimide is mentioned. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, ⁇ - Examples include butyrolactone.
  • an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone are preferable in view of obtaining a resin film having high flatness with good reproducibility.
  • the present invention is a resin thin film forming composition containing the polyimide, silicon dioxide, and an organic solvent.
  • the composition for forming a resin thin film of the present invention is uniform, and phase separation is not recognized.
  • the blending ratio of the crosslinking agent is 0.1 to 200% by mass, preferably 0.2 to 100% by mass, based on the total mass of the polyimide and the silicon dioxide. .
  • the blending amount of the solid content in the composition for forming a resin thin film of the present invention is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass.
  • the solid content concentration is less than 0.5% by mass, the production efficiency of the resin thin film is lowered and the viscosity of the resin thin film forming composition is lowered, so that a coating film having a uniform surface can be obtained. Hateful.
  • the viscosity of the resin thin film forming composition becomes too high, and there is a possibility that the film forming efficiency is deteriorated and the surface uniformity of the coating film is also lacking.
  • solid content here means the total mass of components other than an organic solvent, and even if it is a liquid monomer etc., it shall be included in a weight as solid content.
  • the viscosity of the composition for forming a resin thin film is appropriately set in consideration of the thickness of the resin thin film to be produced. In particular, when the purpose is to obtain a resin thin film having a thickness of about 5 to 50 ⁇ m with good reproducibility. Usually, it is about 500 to 50,000 mPa ⁇ s at 25 ° C., preferably about 1,000 to 20,000 mPa ⁇ s.
  • various other organic or inorganic low-molecular or high-molecular compounds may be blended with the resin thin film-forming composition of the present invention.
  • a catalyst an antifoaming agent, a leveling agent, a surfactant, a dye, a plasticizer, fine particles, a coupling agent, a sensitizer, and the like can be used.
  • the catalyst may be added for the purpose of reducing the retardation and linear expansion coefficient of the resin thin film.
  • the composition for resin thin film formation which contains a catalyst in addition to the said polyimide, silicon dioxide, and an organic solvent can also be made into the object of this invention.
  • composition for forming a resin thin film of the present invention can be obtained by dissolving the polyimide and silicon dioxide obtained by the above-mentioned method in the above-mentioned organic solvent, and adding silicon dioxide to the reaction solution after preparing the polyimide. If desired, the organic solvent may be further added.
  • the organic solvent is removed by applying the composition for forming a resin thin film of the present invention described above to a substrate, drying and heating, high heat resistance, high transparency, moderate flexibility, and moderate line.
  • a resin thin film having an expansion coefficient and low retardation can be obtained.
  • the resin thin film containing the said resin thin film, ie, the said polyimide, and the said inorganic silica compound is also the object of this invention.
  • a resin thin film containing a catalyst in addition to the polyimide and silicon dioxide is also an object of the present invention.
  • the base material used for the production of the resin thin film examples include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene resin, etc.), metal, stainless steel (SUS ), Wood, paper, glass, silicon wafer, slate and the like.
  • plastics polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene resin, etc.
  • metal stainless steel
  • Wood wood, paper, glass, silicon wafer, slate and the like.
  • the base material to be applied is a glass or silicon wafer, and the obtained resin thin film is excellently peeled. It is more preferable that it is glass because it shows the property.
  • a linear expansion coefficient of the base material to apply from a viewpoint of the curvature of the base material after coating, it is 30 ppm / degrees C or less, More preferably, it is more preferable that it is 20 ppm / degrees C or less.
  • the coating method of the resin thin film forming composition on the substrate is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, Examples thereof include a die coating method, an inkjet method, and a printing method (such as a relief plate, an intaglio plate, a planographic plate, and a screen printing), and these can be appropriately used depending on the purpose.
  • the heating temperature is preferably 300 ° C. or lower. If the temperature exceeds 300 ° C., the resulting resin thin film becomes brittle, and a resin thin film particularly suitable for display substrate use may not be obtained. Also, considering the heat resistance and linear expansion coefficient characteristics of the resulting resin thin film, after heating the applied resin thin film forming composition at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased. Finally, it is desirable to heat at over 175 ° C. to 280 ° C. for 30 minutes to 2 hours. Thus, the low thermal expansion characteristic can be expressed by heating at a temperature of two or more stages of drying the solvent and promoting molecular orientation. In particular, the applied composition for forming a resin thin film is heated at 40 ° C.
  • Heating for minutes to 2 hours is preferred.
  • the appliance used for heating include a hot plate and an oven.
  • the heating atmosphere may be under air or under an inert gas such as nitrogen, and may be under normal pressure or under reduced pressure, and different pressures are applied at each stage of heating. May be.
  • the thickness of the resin thin film is usually about 1 to 60 ⁇ m, preferably about 5 to 50 ⁇ m, particularly when used as a substrate for a flexible display.
  • the thickness of the coating film before heating is adjusted to obtain a resin having a desired thickness.
  • a thin film is formed.
  • the method for peeling the resin thin film formed in this way from the substrate is not particularly limited, and the resin thin film is cooled together with the substrate, and a thin film is cut and peeled or tension is applied via a roll. And a method of peeling off.
  • the resin thin film according to a preferred embodiment of the present invention thus obtained can achieve high transparency with a light transmittance of 75% or more at a wavelength of 400 nm. Furthermore, the resin thin film can have a low linear expansion coefficient of, for example, 50 ppm / ° C. or less, particularly 10 ppm / ° C. to 35 ppm / ° C. at 50 ° C. to 200 ° C., and has excellent dimensional stability during heating. It is.
  • the resin thin film has an in-plane retardation R 0 expressed by the product of birefringence (difference between two in-plane orthogonal refractive indexes) and a film thickness when the wavelength of incident light is 590 nm,
  • the film thickness thickness direction retardation R th represented are both featuring a very small.
  • Resin thin film of the present invention when the average film thickness of approximately 15 [mu] m ⁇ 40 [mu] m, less than the retardation R th in the thickness direction is 700 nm, for example 300nm or less, for example, 1 nm ⁇ 300nm, plane retardation R 0 is less than 4, For example, it is 0.1 to 3.9, and the birefringence ⁇ n has a very low value of less than 0.01, for example, 0.0003 to 0.009.
  • the resin thin film of the present invention described above has the above-mentioned characteristics, it satisfies each condition necessary for a base film of a flexible display substrate, and can be particularly suitably used as a base film of a flexible display substrate.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • BODAxx bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride
  • TFMB 2,2′-bis (trifluoromethyl) benzidine
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • the average particle diameter calculated from the specific surface area value measured by the nitrogen adsorption method was 22 nm.
  • the specific surface area of the dry powder of silica sol was measured using a specific surface area measuring device Monosorb MS-16 manufactured by Yuasa Ionics Co., and D was measured using the measured specific surface area S (m 2 / g).
  • Example 1-1 except that instead of 1.428 g of Cymel 303, 1.442 g of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (TMG) (99% purity) was used.
  • TMG 1,3,4,6-tetrakis (methoxymethyl) glycoluril
  • the composition for resin thin film formation was obtained by the same method.
  • Example 1 except that instead of 9.24 g of GBL-M silica sol and 1.428 g of Cymel 303, 3.96 g of GBL-M silica sol and 0.866 g of TEPIC-L (99% purity) were used. 1 was used to obtain a resin thin film forming composition.
  • Example 1-4 Example 1 except that Cymel 303 (purity 100%) 0.594 g and TM-BIP-A (purity 98%) 0.0396 g were used instead of Cymel 303 1.428 g. 1 was used to obtain a resin thin film forming composition.
  • Cymel 303 purity 100%
  • TM-BIP-A purity 98%) 0.0396 g were used instead of Cymel 303 1.428 g. 1 was used to obtain a resin thin film forming composition.
  • Comparative Example 1-A A resin thin film forming composition was obtained in the same manner as in Example 1-1, except that 1.428 g of Cymel 303 was not used.
  • Example 2-1 The composition for forming a resin thin film obtained in Example 1-1 was applied to a glass substrate, and the coating was applied in the air at 50 ° C. for 30 minutes, 140 ° C. for 30 minutes, 200 ° C. for 60 minutes, and then a nitrogen atmosphere. Under heating at 280 ° C. for 60 minutes, a resin thin film was obtained. The obtained thin film was peeled off by mechanical cutting and subjected to subsequent evaluation.
  • Example 2-2 to Example 2-4, Comparative Example 2-A Except for using the resin thin film forming composition obtained in Examples 1-2 to 1-4 and Comparative Example 1-A instead of the resin thin film forming composition obtained in Example 1-1, Each resin thin film was obtained by the same method as described above.
  • Td 5% 5% weight loss temperature
  • Td [°C] 5% weight loss temperature
  • Example 3-1 The thin film (3 cm ⁇ 3 cm rectangular film) obtained in Example 2-1 was immersed in a test solvent at 60 to 70 ° C. for 3 to 5 minutes at room temperature.
  • Examples 3-2 to 3-4, Comparative Example 3-A Using the thin films obtained in Examples 2-2 to 2-4 and Comparative Example 2-A, a solvent immersion test was conducted in the same manner as in Example 3-1. In Examples 3-3 and 3-4, tests were conducted using only TOK106 as a test solvent.
  • Table 1 shows the heat resistance and optical properties of the resin thin films obtained from the respective resin thin film forming compositions
  • Table 2 shows the results of the solvent immersion test.
  • the resin thin film of the present invention has a low coefficient of linear expansion [ppm / ° C.] (50 to 200 ° C.) (less than 35 ppm / ° C.), a high light transmittance [%], As a result, the heat resistance was improved and the yellowness (CIE b * ) was low. Further, the thickness direction retardation Rth was as extremely low as less than 300 nm, the birefringence ⁇ n was also as extremely low as less than 0.01, and it was resistant to various solvents. On the other hand, although the resin thin film of the comparative example had the heat resistance and optical characteristics similar to those of the examples, the result was inferior in solvent resistance.
  • the resin thin film produced using the diamine for the resin thin film forming composition of the present invention has a low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, and excellent solvent resistance. That is, it satisfies the requirements for a base film of a flexible display substrate, and can be expected to be particularly suitably used as a base film of a flexible display substrate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème à résoudre par la présente invention est de préparer une composition de formation d'un film fin en résine, pour l'obtention d'un film fin en résine, particulièrement un film fin en résine qui convient comme substrat pour un dispositif souple, moyennant quoi le film fin en résine non seulement présente une résistance à la chaleur et une résistance aux solvants excellentes, mais également possède la caractéristique d'une fonction retard faible. La solution selon l'invention est : une composition de formation d'un film fin en résine, comprenant un polyimide, des particules de dioxyde de silicium présentant un diamètre moyen de particule de 100 nm ou moins calculé à partir d'une surface spécifique mesurée par l'intermédiaire d'un procédé d'adsorption d'azote, un agent de réticulation, et un solvant organique ; et un film fin en résine formé à partir de la composition de formation d'un film fin en résine.
PCT/JP2016/079145 2015-09-30 2016-09-30 Composition pour la formation d'un film fin en résine WO2017057741A1 (fr)

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JP7116366B2 (ja) 2017-06-08 2022-08-10 日産化学株式会社 フレキシブルデバイス用基板の製造方法
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CN109765729A (zh) * 2017-11-09 2019-05-17 住友化学株式会社 光学膜
JP2019194343A (ja) * 2017-11-09 2019-11-07 住友化学株式会社 光学フィルム
JP7257901B2 (ja) 2017-11-09 2023-04-14 住友化学株式会社 光学フィルム
JP2019194296A (ja) * 2017-11-09 2019-11-07 住友化学株式会社 光学フィルム
WO2024005021A1 (fr) * 2022-06-30 2024-01-04 富士フイルム株式会社 Composition, film de transfert, procédé de production de stratifié, stratifié et procédé de production d'un boîtier de semi-conducteur

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