WO2020067467A1 - Liquide d'application filmogène planarisé, procédé de production de liquide d'application filmogène planarisé, feuille métallique pourvue d'un film planarisé, procédé de production d'une feuille métallique pourvue d'un film planarisé - Google Patents

Liquide d'application filmogène planarisé, procédé de production de liquide d'application filmogène planarisé, feuille métallique pourvue d'un film planarisé, procédé de production d'une feuille métallique pourvue d'un film planarisé Download PDF

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WO2020067467A1
WO2020067467A1 PCT/JP2019/038250 JP2019038250W WO2020067467A1 WO 2020067467 A1 WO2020067467 A1 WO 2020067467A1 JP 2019038250 W JP2019038250 W JP 2019038250W WO 2020067467 A1 WO2020067467 A1 WO 2020067467A1
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flattening film
forming
coating liquid
metal foil
phenylsilsesquioxane
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PCT/JP2019/038250
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English (en)
Japanese (ja)
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山田　紀子
左和子 山口
裕 関口
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日本製鉄株式会社
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Priority to JP2020549456A priority Critical patent/JP7047927B2/ja
Publication of WO2020067467A1 publication Critical patent/WO2020067467A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the present disclosure relates to a coating liquid for forming a flattening film, a method for manufacturing a coating liquid for forming a flattening film, a metal foil coil with a flattening film, and a method for manufacturing a metal foil coil with a flattening film.
  • Process temperatures for producing electronic devices differ depending on the type and constituent materials of the electronic device. For example, when a TFT liquid crystal display of amorphous silicon or low-temperature polysilicon (LTPS) is formed, a process temperature of about 300 ° C. to 400 ° C. is required. Therefore, the insulating film covering the metal foil is required to have heat resistance that can withstand up to 400 ° C.
  • LTPS low-temperature polysilicon
  • the film material for coating the metal foil examples include an inorganic / organic hybrid material.
  • an organic-modified silica film is typical. Since the organic-modified silica film contains an organic group, it is more flexible than an inorganic film. For this reason, the film thickness can be increased.
  • the organic modified silica film has a main skeleton formed of an inorganic skeleton of Si—O. Therefore, the heat resistance of the organically modified silica film is determined by the decomposition temperature of the organic group modifying the main skeleton. If a methyl group or a phenyl group is selected as the organic group, the organically modified silica film can secure heat resistance of about 400 ° C.
  • the silica film modified with a phenyl group has its Si—O main skeleton hydrolyzed even at high temperature and high humidity (for example, at 85 ° C. and 85% RH environment acceleration test) due to the high hydrophobicity of the phenyl group. Difficult and excellent in moisture resistance. For this reason, a metal foil coated with a phenyl group-modified silica film is preferable as a substrate for an electronic device.
  • Patent Documents 1 to 5 Materials for forming the organically modified silica film are disclosed, for example, in Patent Documents 1 to 5.
  • Patent Documents 3 to 5 disclose coating liquids for forming an organically modified silica film covering a metal foil.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2008-81736
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-226755
  • Patent Document 3 International Patent Application Publication No. WO 2016/076399
  • Patent Document 4 Japanese Patent Application Publication No. 2018-123192
  • Patent Document 5 Japanese Patent Application Publication No. 2018-062582
  • Patent Document 3 a phenylsiloxane ladder polymer is produced by distilling a solution containing phenyltrialkoxysilane hydrolyzed in an organic solvent under reduced pressure. Then, it is dissolved in toluene or the like to synthesize a coating solution. In this method, the alkoxy groups that could not be completely hydrolyzed and the alcohol that could not be completely removed by distillation under reduced pressure remain in the coating solution as they are.
  • a flexible substrate for example, when a metal foil with a flattening film provided on a metal foil with a flattening film made of an organic-modified silica film disclosed in Patent Document 3 is applied to an electronic device, the life of the electronic device element is reduced.
  • the coating solution by the synthesis method described in Patent Documents 4 and 5 is synthesized by the same process as the coating solution of Patent Document 3. Therefore, in an electronic device manufactured on a substrate flattened with a coating liquid described in Patent Documents 4 and 5, the lifetime of the electronic device element may be shortened by alcohol generated by hydrolysis of an alkoxy group.
  • An object of the present disclosure is to provide a coating solution for forming a flattening film, a method for manufacturing a coating solution for forming a flattening film, and a flattening film, which can provide a flattening film in which generation of alcohol is suppressed even in a high-temperature and high-humidity environment
  • An object of the present invention is to provide a method for producing a metal foil with a passivation film and a metal foil with a flattening film.
  • An organic solvent that is immiscible with water, and a phenylsilsesquioxane soluble in the organic solvent, a coating liquid for forming a flattening film The viscosity of the coating liquid when the solid concentration of the phenylsilsesquioxane is 30% by mass and the liquid temperature is 25 ° C. is 2.5 mPa ⁇ s to 35 mPa ⁇ s, The content of the alkoxy group bonded to Si in the phenylsilsesquioxane is 0 to 5% based on all the bonds of Si. Coating liquid for forming flattening film.
  • the alkoxy group bonded to Si in the phenylsilsesquioxane is at least one selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group,
  • the content of the alcohol with respect to Si in the phenylsilsesquioxane is 0 to 2.5 mol%,
  • the amount of the acetic acid is 0.1 mol to 1 mol with respect to 1 mol of the phenyl trialkoxysilane, and the amount of the organotin is 0.005 mol to 0 mol with respect to 1 mol of the phenyl trialkoxysilane. 0.05 moles, The method for producing a coating liquid for forming a flattening film according to [5] or [6].
  • Metal foil A flattening film provided on at least one surface of the metal foil, the flattening film comprising a cured product of the coating solution for forming a flattening film according to any one of [1] to [4]; Having, Metal foil with flattening film.
  • the metal foil is a stainless steel foil, The metal foil with a flattening film according to [8].
  • a flattening film in which the generation of alcohol is suppressed can be obtained, a coating solution for forming a flattening film, a method for manufacturing a coating solution for forming a flattening film, and flattening.
  • a method for producing a metal foil with a passivation film and a metal foil with a flattening film is provided.
  • FIG. 1 is a schematic diagram illustrating an example of a film forming apparatus applied to manufacture a metal foil with a planarizing film according to the present disclosure.
  • 1 is a schematic partial cross-sectional view illustrating an example of a metal foil with a flattening film according to the present disclosure.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • an upper limit or a lower limit described in a certain numerical range may be replaced with an upper limit or a lower limit of another numerical range described in a stepwise manner.
  • the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in the embodiment.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition.
  • the term “step” is included in the term as well as an independent step, even if it cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved.
  • the coating liquid for forming a flattening film according to the present disclosure is a coating liquid for forming a flattening film containing an organic solvent immiscible with water and phenylsilsesquioxane soluble in the organic solvent.
  • the viscosity of the coating liquid when the solid content concentration of phenylsilsesquioxane is 30% by mass and the liquid temperature is 25 ° C. is 2.5 mPa ⁇ s to 35 mPa. S, and the content of the alkoxy group bonded to Si in the phenylsilsesquioxane is 0 to 5% based on all the bonds of Si.
  • phenylsilsesquioxane is a compound that is soluble in a water-immiscible organic solvent.
  • a phenylsilsesquioxane that is soluble in a water-immiscible organic solvent is a phenylsilsesquioxane that is soluble in a water-immiscible organic solvent at 25 ° C. that is 70% by mass or more. Represents Sun.
  • phenylsilsesquioxane is used in an amount of alcohol, phenyltrialkoxysilane, acetic acid, organic tin, and 1 mol of phenyltrialkoxysilane. After mixing and hydrolyzing 2 to 14 times by mole of water, the alcohol is distilled off under reduced pressure, and the resulting dehydration-condensation reaction containing phenylsilsesquioxane is not mixed with water.
  • the compound is preferably a compound which is dissolved in an organic solvent and heated and refluxed at a temperature equal to or higher than the boiling point of the organic solvent immiscible with water, and further dehydration-condensed to further increase the molecular weight.
  • a dehydration-condensation reaction product containing phenylsilsesquioxane is obtained by hydrolyzing phenyltrialkoxysilane in a mixed solution containing alcohol, phenyltrialkoxysilane, acetic acid, organotin, and water, and then hydrolyzing the phenyltrialkoxysilane. Obtained by a dehydration condensation reaction of alkoxysilane.
  • Phenylsilsesquioxane produced by hydrolyzing phenyltrialkoxysilane has been known as a material for the organically modified silica film.
  • Phenylsilsesquioxane is a polymer whose main chain skeleton is composed of Si—O bonds, and has a structure represented by [(RSiO 1.5 ) n ] having a phenyl group in at least a part of R.
  • the structure of this polymer depends on the catalyst and the synthesis conditions, and cage, ladder, and random structures are known.
  • Patent Literature 1 discloses a ladder type in which, after hydrolyzing a silane compound, an organic solvent that generates an azeotropic compound with water is added, heated to reflux, and then water is removed by azeotropic distillation.
  • a method for producing polysilsesquioxane is disclosed.
  • Patent Document 2 discloses that a thermoplastic polyphenylsilsesquioxane having a ladder-type structure is obtained by hydrolyzing phenyl trialkoxysilane with an acid and then proceeding with a condensation reaction using a basic catalyst. It has been disclosed.
  • Patent Documents 1 and 2 disclose only the production of ladder-type silsesquioxane. Since the main purpose of the coating liquid for forming a flattening film of the present disclosure is to obtain a flattening film in which the generation of alcohol is suppressed, the technique is different from those disclosed in these documents.
  • Patent Document 3 discloses a coating liquid for forming a flattening film in which phenylsilsesquioxane is formed using phenyltrialkoxysilane, and the phenylsilsesquioxane is dissolved in an aromatic hydrocarbon-based solvent.
  • the coating liquid for forming a supported film disclosed in Patent Document 3 is obtained, for example, as follows. First, phenyl trialkoxysilane is hydrolyzed in alcohol using acetic acid and organotin as catalysts. Thereafter, the mixture is refluxed at 80 ° C. for 3 hours under a nitrogen stream, and phenylsilsesquioxane obtained by distillation under reduced pressure at a temperature of 160 ° C. to 210 ° C. is dissolved in toluene. When phenylsilsesquioxane is dissolved in toluene, a polymer having a high molecular weight of tens of thousands in terms of styrene is obtained.
  • This polymer is considered to have a ladder structure because of its spinnability and reflow properties. After dissolving in toluene and performing steps such as filtration, a coating liquid for forming a flattening film containing phenylsilsesquioxane is obtained.
  • the coating liquid for forming a flattening film containing phenylsilsesquioxane disclosed in Patent Document 3 it is possible to provide a flattening film on a metal foil.
  • the coating liquid for forming a flattening film disclosed in Patent Document 3 is useful in that a flattening film can be provided by a Roll-to-Roll process, so that it can be cured in a short time.
  • the coating liquid for forming a flattening film obtained as described above is applied on a metal foil, dried at 20 ° C. to 150 ° C., and heat-treated at 400 ° C. to produce a metal foil with a flattening film. I do. Then, an organic EL lighting element is provided as a flexible device element on the flattening film of the metal foil with the flattening film, and sealed with a glass cap. However, it was found that the lifetime of the organic EL lighting element was shortened when left in a high temperature and high humidity environment.
  • the flexible substrate is sealed with a sealing material and provided to a flexible device.
  • a sealing material for sealing the flexible substrate.
  • a small amount of moisture (water vapor) infiltrates.
  • water vapor water vapor
  • the intrusion of moisture becomes remarkable.
  • an organic EL lighting element is provided on a flattening film of a metal foil with a flattening film and sealed with a sealing material, infiltration of moisture becomes remarkable under a high-temperature and high-humidity environment.
  • Groups eg, ethoxy groups
  • alcohol eg, ethanol
  • Some components constituting the organic EL lighting element are soluble in alcohol.
  • phenyltrialkoxysilanes produced by the synthesis methods described in Patent Documents 4 and 5 also have a large amount of alkoxy groups remaining. Therefore, the alkoxy group remains in the flattening film using phenyl trialkoxysilane formed by the synthesis method described in Patent Documents 4 and 5, and the device life is shortened.
  • the amount of the alkoxy group bonded to Si in the phenylsilsesquioxane is sufficiently reduced to a level that suppresses the performance deterioration of the organic semiconductor. I have. That is, when the content of the alkoxy group is 0 to 5% of the total bonds of Si, the device life is improved.
  • the flattening film obtained by using the coating solution for forming a flattening film of the present disclosure no alkoxy group is present, or even if an alkoxy group is present, the amount thereof is small. For this reason, even in a high-temperature and high-humidity environment, generation of alcohol in the flattening film is suppressed. As a result, it is possible to suppress a reduction in the life of the flexible device element.
  • the coating liquid for forming a planarizing film according to the present disclosure includes an organic solvent that is immiscible with water, and phenylsilsesquioxane that is soluble in the organic solvent.
  • the coating liquid for forming a flattening film according to the present disclosure is, for example, mixed with a predetermined material (mixed with alcohol, phenyl trialkoxysilane, acetic acid, organotin, and water) and hydrolyzed. It is obtained by dissolving a dehydration-condensation reaction product obtained by distillation under reduced pressure in an organic solvent immiscible with water.
  • organic solvent immiscible with water examples include aromatic hydrocarbons, ketones, and ethers.
  • aromatic hydrocarbons such as toluene, xylene (o-xylene, m-xylene, p-xylene), trimethylbenzene; MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), cyclohexanone, cyclopentane Ketones such as nonone; ethers such as diethyl ether and diisopropyl ether; and cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane.
  • the organic solvents may be used alone or in combination of two or more.
  • the “organic solvent immiscible with water” is a concept including an organic solvent having low miscibility with water, and represents an organic solvent having a solubility in water of 300 g / L or less.
  • the solubility in water indicates the weight of an organic solvent soluble in 1 L of water at 25 ° C. in units of g / L.
  • the organic solvent that is immiscible with water is ideally an organic solvent having a solubility in water at 25 ° C. of 30 g / L or less.
  • the phenyl trialkoxysilane is not particularly limited.
  • phenyltriethoxysilane is preferred from the viewpoint of being industrially mass-produced and easily available.
  • Alcohol is used when hydrolyzing phenyl trialkoxysilane.
  • the alcohol is not particularly limited, and examples thereof include methanol, ethanol, propanol (n-propanol, iso-propanol), and butanol (n-butanol, iso-butanol).
  • Acetic acid and organotin are each catalysts.
  • Acetic acid is a catalyst that promotes hydrolysis.
  • Organotin is a catalyst that promotes phenyltrialkoxysilane and its dehydration-condensation reaction after hydrolysis.
  • organic tin examples include dibutyltin diacetate, bis (acetoxydibutyltin) oxide, dibutyltinbisacetylacetonate, monobutylester dibutyltinbismaleate, monobutylester dioctyltinbismaleate, and bis (lauroxydibutyltin) oxide. .
  • dibutyltin diacetate and dibutyltin bisacetylacetonate are particularly preferable as the organic tin.
  • the water is not particularly limited, and includes, for example, distilled water, ion-exchanged water, ultrafiltration water, pure water and the like.
  • the coating liquid for forming a flattening film according to the present disclosure has the following characteristics.
  • the viscosity of the coating liquid for forming a flattening film according to the present disclosure is 2.5 mPa ⁇ s to 35 mPa ⁇ s.
  • the viscosity of the coating liquid is the viscosity of the coating liquid when the solid content concentration of phenylsilsesquioxane is 30% by mass and the liquid temperature is 25 ° C.
  • the solid content concentration is 30% by mass and the viscosity at a temperature of 25 ° C. is in this range, it is preferable from the viewpoint of coating properties when forming a flattening film and from the viewpoint of storage stability.
  • the weight average molecular weight in terms of styrene of phenylsilsesquioxane is low, which is generally less than 5000. Therefore, even if the solid content concentration is increased, the viscosity cannot be increased, resulting in poor coatability. Therefore, a desired film thickness cannot be obtained. Further, a rapid dehydration / condensation reaction occurs due to the heat treatment, which causes a large volume shrinkage, so that the flattening film is easily cracked.
  • the method of measuring the viscosity of the coating liquid for forming a flattening film is as follows. First, the solid content concentration of phenylsilsesquioxane in the coating liquid for forming a flattening film is adjusted to 30% by mass, and the liquid temperature of the coating liquid is adjusted to 25 ° C. Next, the viscosity of the coating liquid whose solid content concentration and liquid temperature have been adjusted is measured using a VISCOMATE @ VM-10A vibrating viscometer manufactured by CBC Corporation.
  • the weight average molecular weight in terms of styrene of phenylsilsesquioxane was 5,000 to 100,000.
  • the phenylsilsesquioxane can be confirmed to exhibit spinnability.
  • the infrared absorption spectrum (IR) of phenylsilsesquioxane was measured, a double peak derived from a siloxane bond was shown at a wavenumber of about 1100 cm -1 .
  • phenylsilsesquioxane contained in the coating liquid for forming a flattening film of the present disclosure has a ladder-type structure. That is, phenylsilsesquioxane is presumed to have a ladder structure in the following points. 1) it is dissolved in an organic solvent, 2) phenylsilsesquioxane having a weight average molecular weight in terms of styrene of 5,000 to 100,000; 3) The point where phenylsilsesquioxane after evaporating the organic solvent exhibits spinnability. 4) The point where IR shows a double peak derived from a siloxane bond at a wavenumber of about 1100 cm -1 .
  • the content of the alkoxy group bonded to Si in phenylsilsesquioxane is 0 to 5% based on all the bonds of Si. That is, the amount of -Si-OR groups (R: methyl group, ethyl group, propyl group, etc.) bonded to Si in the phenylsilsesquioxane is 5% or less (total bonds to Si).
  • R methyl group, ethyl group, propyl group, etc.
  • the lower limit of the content of the alkoxy group bonded to Si in phenylsilsesquioxane is 0%.
  • the upper limit of the content of the alkoxy group may be 3% or less, 2% or less, or 1% or less.
  • the alkoxy group may be at least one selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group, depending on the phenyl trialkoxysilane used.
  • the alkoxy group may be an ethoxy group.
  • the content of the alkoxy group bonded to Si is a value measured by NMR. Specifically, it is measured as follows.
  • phenylsilsesquioxane was synthesized from phenyltriethoxysilane as a raw material in a toluene solvent, and the coating liquid for forming a flattening film according to the present disclosure prepared by adjusting the solid content concentration of phenylsilsesquioxane to 30% by mass was used.
  • An example will be described.
  • phenyltrialkoxysilane other than phenyltriethoxysilane is used as a raw material, or when a solvent other than toluene is used, the peak positions of NMR spectra and the like are different, but the concepts of measurement and calculation are the same.
  • FIG. 1 shows the structures of T 1 , T 2 , and T 3 in phenylsilsesquioxane. From the 13 C NMR spectrum, the presence of toluene, ethanol, Si-Ph groups, and Si-OEt groups is indicated by peaks at 20.4 ppm, 57.1 ppm, 133.7 ppm, and 58.1 ppm. From the peak area ratio, the abundance ratio of each component is calculated as 388.2 mol%, 2.0 mol%, 100 mol%, and 13.1 mol%, respectively. It is calculated so that the mol% of Si-Ph becomes 100. In the case where the peak is buried in the background and no peak is observed in the NMR spectrum, it is considered that the corresponding component does not exist.
  • the terminal groups are of two types: a Si—OH group and a Si—OEt group.
  • Si When Si is 1, T 1 has two terminal groups and T 2 has one terminal group.
  • the ratio of the Si—OEt group is a and the ratio of the Si—OH group is 1 ⁇ a
  • the number of phenyl groups and Si are the same, and therefore, when Si is 100, there are 100 phenyl groups.
  • the abundance ratio (molar ratio) of the phenyl group to the ethoxy group is known to be 100: 13.1, so a is 0.277. Therefore, the breakdown of 11.8% of the terminal groups is 3.3% of Si—OEt groups and 8.5% of Si—OH groups.
  • the content of the Si-OEt group with respect to all the bonds of Si of the phenylsilsesquioxane in the coating solution measured as described above can be estimated to be 3.3%.
  • the content of alcohol with respect to Si in phenylsilsesquioxane is preferably 0 to 2.5 mol%.
  • the alcohol content is 2.5 mol% or less, poor coating (voids, uneven coating, etc.) is suppressed.
  • the upper limit of the alcohol content is more preferably 1.5 mol% or less, and further preferably 0.5 mol% or less.
  • the alcohol content is most preferably 0 mol% (that is, it is most preferable that the coating solution does not contain alcohol).
  • Examples of a method for producing a coating liquid having an alcohol content within the above range include a method for producing a coating liquid for forming a flattening film (method for producing phenyltrialkoxysilane) described later.
  • a method for producing a coating liquid for forming a flattening film method for producing phenyltrialkoxysilane described later.
  • phenyl trialkoxysilane is produced by the synthesis methods described in Patent Documents 3 to 5
  • a certain amount of alcohol remains in the coating solution.
  • the alcohol is exemplified by methanol, ethanol, and propanol.
  • the alcohol content is measured by a 13 C NMR spectrum.
  • the content of ethanol as an alcohol is calculated to be 2.0 mol%, based on the peak area ratio of 57.1 ppm and 133.7 ppm in 13 C NMR measurement, where the Si-Ph group is 100 mol%.
  • Solids contained in the coating liquid of the present disclosure is ideally phenyl silsesquioxane, namely from those represented as PhSi [theta] 3/2, ethanol when the Si in the coating liquid was 100 mol%
  • the content is 2.0 mol%.
  • the content of alcohol other than ethanol is also calculated from the peak area ratio in 13 C NMR measurement.
  • the method for producing a coating liquid for forming a planarizing film according to the present disclosure includes the following steps.
  • a step of evaporating the alcohol under reduced pressure to advance the dehydration condensation reaction to generate a dehydration condensation reaction product containing phenylsilsesquioxane (concentration step).
  • hydrolysis step it is preferable to carry out hydrolysis by mixing organotin, acetic acid, and water with respect to phenyl trialkoxysilane in alcohol.
  • it may be performed as follows. First, a mixed solution of alcohol and phenyl trialkoxysilane is prepared. Next, organotin and acetic acid are mixed with this mixed solution, and water is further mixed to hydrolyze phenyltrialkoxysilane. A mixture of alcohol, phenyl trialkoxysilane, and organotin may be mixed with acetic acid and further mixed with water.
  • the hydrolysis may be performed by mixing a first mixed solution in which alcohol, phenyl trialkoxysilane, and organotin are mixed, and a second mixed solution in which acetic acid and water are mixed. Reflux may be performed at about 80 ° C. under a nitrogen stream to promote the hydrolysis reaction.
  • the amount of acetic acid is preferably in the range of 0.1 mol to 1 mol based on 1 mol of phenyltrialkoxysilane.
  • the amount of acetic acid is 0.1 mol or more per 1 mol of phenyltrialkoxysilane, the molecular weight of phenylsilsesquioxane increases. Even if the amount of acetic acid exceeds 1 mol, the effect of increasing the molecular weight is saturated.
  • the amount of the organotin is preferably 0.005 mol to 0.05 mol per 1 mol of phenyltrialkoxysilane from the viewpoint of accelerating the polycondensation reaction of phenylsilsesquioxane.
  • the amount of the organotin is 1 mol or more per 1 mol of the phenyl trialkoxysilane, the condensation reaction of the phenylsilsesquioxane during the heat treatment after the application on the metal foil is promoted. In addition, cracks hardly occur in the flattening film.
  • the amount is less than 0.05 mol, gelation of phenylsilsesquioxane hardly occurs at the stage of hydrolysis before distillation under reduced pressure.
  • the amount of water used for the hydrolysis is 1 mole of phenyltrialkoxysilane.
  • the molar ratio is 4.2 to 14 times.
  • the preferred amount of water is 4.5 to 13.5 moles.
  • the concentration step the alcohol is distilled off under reduced pressure, and the dehydration condensation reaction proceeds to generate a dehydration condensation reaction product containing phenylsilsesquioxane.
  • the concentration step it is preferable to distill off the alcohol while heating the solution containing the hydrolyzed phenyltrialkoxysilane to a temperature of 30 ° C. to 90 ° C. under reduced pressure.
  • a product obtained by partially dehydrating and condensing phenyltrialkoxysilane that has been hydrolyzed almost 100% is obtained.
  • the temperature, the degree of reduced pressure, and the time of the partial dehydration condensation reaction be adjusted to advance the dehydration condensation reaction.
  • the weight is adjusted to be 1.04 times to 1.11 times.
  • the concentration step at the time of completion, the alcohol is almost removed and the state becomes almost solventless. Therefore, if the hydrolyzed molecules collide with each other, dehydration condensation easily proceeds even if there is steric hindrance. Therefore, an oligomer containing a large amount of the aforementioned T 1 and T 2 (see FIG. 1) is likely to be generated. When such oligomers are dehydrated and condensed, an undesirable reaction occurs in the step of increasing the molecular weight. For this reason, it is preferable that the oligomer does not become a large oligomer in the concentration step.
  • the average molecular weight of the dehydration-condensation reaction product is 1.04 to 1.11 times the average molecular weight of 129 of C 6 H 5 SiO 3/2 , the monomer of the hydrolyzate of phenyl trialkoxysilane , And a mixture of a dimer and an oligomer.
  • the step of increasing the molecular weight it is preferable to dissolve the partial dehydration-condensation reaction product in an organic solvent immiscible with water so that the solid content concentration is 30% by mass to 80% by mass. Further, it is preferable that the reflux time is 3 hours to 30 hours at a temperature not lower than the boiling point of the organic solvent immiscible with water.
  • the heating and refluxing is preferably performed while removing alcohol together with water using a Dean-Stark trap, so that a partial dehydration / condensation reaction between dehydration / condensation products proceeds.
  • the partial dehydration condensation product is an oligomer containing a large amount of T 1 and T 2
  • a monomer or a dimer is sequentially added to an oligomer having no silanol group by a dehydration condensation reaction.
  • the coating liquid for forming a flattening film according to the present disclosure is obtained.
  • the metal foil with a flattening film according to the present disclosure has a metal foil and a flattening film provided on at least one surface of the metal foil and obtained by curing the coating liquid for forming a flattening film according to the present disclosure.
  • an example of a preferable manufacturing method for obtaining the metal foil with a flattening film according to the present disclosure includes the following steps. A step of applying the coating liquid for forming a flattening film of the present disclosure to at least one surface of the metal foil (coating step). After reflow and film curing in a temperature range of 300 ° C. to 450 ° C. in an inert gas atmosphere, a winding step (winding step).
  • the flattening film is provided on at least one surface of the metal foil. That is, the flattening film may be provided on both sides of the rolled surface of the metal foil, or may be provided only on one side of the rolled surface. In general, electronic device elements (for example, organic EL lighting elements) are often manufactured only on one side of a substrate. Therefore, the flattening film may be provided only on one side of the metal foil.
  • the metal foil Since the metal foil is thinned by rolling, streaks are observed in the rolling direction. In addition, there are flaws elongated in the rolling direction due to inclusions included in the original molten metal, foreign matters caught in the rolling rolls, and the like.
  • the size of the flaw is, for example, often about several tens ⁇ m in width and about 1 mm to several mm in length.
  • the surface roughness of the metal foil differs between the direction parallel to the rolling streaks and the direction perpendicular to the rolling streaks, and the vertical direction has a larger surface roughness. Therefore, for the purpose of improving the flatness of the metal foil by covering the flattening film, attention is paid to the vertical direction in which the surface roughness is the largest. Specifically, the surface roughness was measured at a measurement length of 1.25 mm with a stylus type roughness meter at 10 or more points perpendicular to the rolling direction of the metal foil, that is, in the width direction of the metal foil, and the average value was measured. Is adopted.
  • the relationship between the surface roughness of the metal foil with a flattening film and the characteristics of the organic EL element as a flexible device element formed thereon was examined in detail. As a result, it was found that the flatness of the film surface was important in reducing the leak current of the organic EL element. If the arithmetic average roughness Ra in the direction perpendicular to the rolling direction of the surface of the metal foil with a flattening film is 30 nm or less, the leak current of the organic EL light emitting element is set to a practical level of 1E-4 A / m 2 or less. be able to.
  • the leak current of the device is formed by forming a lower electrode, a light emitting portion, and an upper electrode of the device in this order on a flattened film of phenylsilsesquioxane to produce a device, and applying 3 V between the lower electrode and the upper electrode. It is determined by dividing the current when a voltage is applied by the element area.
  • the light emitting section is composed of a plurality of layers, and the total thickness is about 100 nm to 150 nm. When the surface of the film is rough, a portion where the distance between the lower electrode and the upper electrode is short is formed, and the leak current of the element increases.
  • Ra of the metal foil with a flattening film exceeds 30 nm, an element having a large leak current exceeding 1E-4 A / m 2 is obtained. As a result, phenomena such as a reduction in the efficiency of the element and a short circuit occur.
  • a more preferable range of Ra is 20 nm or less, and further preferably 15 nm or less. By setting Ra within this range, a smaller leak current can be obtained.
  • the arithmetic average roughness Ra in the direction perpendicular to the rolling direction of the surface of the metal foil with a flattening film is preferably as small as possible, and the lower limit of Ra is not limited. Ra may be, for example, 0.5 nm or more.
  • An insulating coating may be provided on at least one surface of the metal foil.
  • the type of the insulating coating is not particularly limited, and examples thereof include metal oxides (silica, alumina, and the like), inorganic salts (aluminum phosphate, calcium phosphate, and the like), and heat-resistant resins (polyimide, polytetrafluoroethylene, and the like).
  • the insulating film made of a metal oxide can be formed by, for example, a method such as sputtering, vapor deposition, or CVD.
  • the inorganic salt insulating film can be formed by a coating method such as a roll coater or a spray.
  • the insulating film of the heat-resistant resin can be formed by a coating method such as a comma coater, a die coater, and a spray.
  • the metal foil is not particularly limited, and examples thereof include an aluminum foil, a copper foil, a titanium foil, and a stainless steel foil. Among these, stainless steel foil is preferable.
  • Stainless steel foil is suitable as a flexible substrate for electronic devices from the viewpoint that it is industrially easy to manufacture at low cost and hardly breaks. When a stainless steel foil is used, the reflectivity of the stainless steel foil is low (the reflectivity is 60%), so that a reflective film may be formed on at least one surface of the stainless steel foil.
  • the stainless steel foil may be any of austenitic, ferrite and martensitic stainless steel foils. From the viewpoint of application to a flexible substrate, an austenitic or ferritic stainless steel foil is preferable.
  • the thickness of the metal foil is not particularly limited, and may be, for example, 10 ⁇ m to 100 ⁇ m.
  • an organic EL lighting an organic EL display or the like of top emission is manufactured using a transparent lower electrode as an electronic device
  • light is repeatedly reflected on the surface of the stainless steel foil. If the reflectance of the stainless steel foil is about 60%, much light is lost and the efficiency of the device is reduced.
  • a reflective film for example, a reflectance of about 95%) is formed on the surface of the stainless steel foil, most of the light is reflected by the reflective film, so that the efficiency of the device is significantly improved.
  • examples of the type of the reflective film having a high reflectance of about 95% include pure Al, an Al alloy, pure Ag, and an Ag alloy.
  • the Al alloy include Al-Si and Al-Nd alloys.
  • Ag alloys include alloys such as Ag-Nd and Ag-In.
  • the reflection film can be formed by a sputtering method or the like.
  • the thickness of the flattening film is preferably 2.0 ⁇ m to 5.0 ⁇ m from the viewpoint of flattening the film and suppressing cracks.
  • the thickness of the flattening film is 2.0 ⁇ m or more, it is easy to cover the unevenness of the metal foil. From the viewpoint of covering the unevenness of the metal foil, the thickness of the flattening film is preferably 2.5 ⁇ m or more.
  • the thickness of the flattening film is 5 ⁇ m or less, cracking of the flattening film is suppressed. Further, not only cracks during film formation but also cracks when the stainless steel foil covered with the flattening film is bent as a flexible substrate are suppressed.
  • the thickness of the flattening film is more preferably equal to or less than 4.5 ⁇ m, and still more preferably equal to or less than 4.0 ⁇ m.
  • FIG. 2 is a schematic diagram illustrating an example of a film forming apparatus applied to manufacture the metal foil with a flattening film according to the present disclosure.
  • This film forming apparatus represents a continuous film forming apparatus for providing a flattening film on one side of a metal foil by a Roll to Roll process.
  • the film forming apparatus 100 shown in FIG. 2 contains a coil unwinding unit 12 that unwinds a metal foil wound in a coil shape and a coating liquid 22A for forming a flattening film according to the present disclosure.
  • a coil winding unit 14 for winding the attached metal foil.
  • the support roll supporting the metal foil is arranged so as not to contact the film surface (the dried film surface and the cured film surface) on the electronic device formation side.
  • the film forming apparatus 100 includes a tension applying roll 32A and a tension applying roll 32B so that wrinkles and the like do not occur when the film is conveyed.
  • the tension applying roll 32 ⁇ / b> A is provided on the upstream side of the application unit 22 in the metal foil transport direction, and stabilizes the transport of the metal foil.
  • the tension applying roll 32B is provided on the downstream side of the heat treatment unit 26 and on the upstream side of the coil winding unit 14, and stabilizes the transport of the metal foil with the flattening film.
  • the application step is a step of applying the coating liquid for forming a flattening film according to the present disclosure.
  • the metal foil wound around the core is attached to the coil unwinding section 12.
  • the metal foil is unwound from the coil unwinding unit 12 in the direction of arrow A.
  • the transport of the metal foil is stabilized by passing through the tension applying roll 32A, and the metal foil is sent to the coating unit 22 in which the coating liquid 22A for forming a flattening film of the present disclosure is stored.
  • the coating roll applies the flattening film forming coating liquid 22A to one surface of the metal foil to form a coating film of the flattening film forming coating liquid 22A.
  • the winding step is a step of winding after drying, heat treatment, and cooling after application.
  • the metal foil provided with the coating film of the coating liquid 22A for forming a flattening film is sent to the drying unit 24.
  • the drying unit 24 the solvent and moisture contained in the coating film are removed, and the coating film becomes a dried film.
  • the metal foil on which the dried film of the coating liquid 22A for forming a flattening film is formed is sent from the drying unit 24 to the heat treatment unit 26.
  • the heat treatment section 26 the surface of the dried film is flattened by being reflowed.
  • the metal foil on which the cured film of the coating liquid 22A for forming a flattening film (that is, the flattening film) is formed is sent from the heat treatment unit 26 to the cooling unit 28.
  • cool air is blown from a cooling body 28 ⁇ / b> A arranged on the surface side where the cured film is provided and a cooling body 28 ⁇ / b> B arranged on the opposite surface side (that is, the metal foil surface side) to be cooled.
  • the metal foil with the flattening film is sent from the cooling unit 28 to the coil winding unit 14.
  • the transport of the metal foil with the flattening film is stabilized by passing through the tension applying roll 32A.
  • the metal foil with the flattening film is transported in the direction of arrow A, and is wound around the core by the coil winding unit 14.
  • FIG. 3 is a schematic partial cross-sectional view showing a part of the metal foil with a flattening film, showing the metal foil with a flattening film according to the present disclosure.
  • the metal foil 300 with a flattening film shown in FIG. 3 includes a metal foil (metal foil) 302 and a flattening film 304 provided on one surface of the metal foil 302.
  • the transport speed (sheet passing speed) of the metal foil is not particularly limited, and is, for example, about 1 m / min to 20 m / min. The higher the transfer speed, the higher the productivity.
  • the method of applying the coating liquid for forming a flattening film to the surface of the metal foil in the coating section is not particularly limited.
  • the coating method include various coating methods (spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method) Method, spray coating method, nozzle coating method, etc.) and various printing methods (gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc.).
  • the drying section dries the coating film on the metal foil and removes the solvent and moisture from the coating film to form a dried film.
  • the drying treatment is preferably performed at a temperature of 20 ° C to 150 ° C.
  • the drying time is preferably about 0.5 to 2 minutes.
  • the atmosphere in the drying unit may be the air or an inert gas atmosphere (for example, a nitrogen gas atmosphere). If the drying temperature is higher than the synthesis temperature of phenylsilsesquioxane by distillation under reduced pressure, the ladder-type structure of phenylsilsesquioxane may be softened. For this reason, the drying temperature is preferably lower than the synthesis temperature of phenylsilsesquioxane.
  • the phenylsilsesquioxane In the dried film, the phenylsilsesquioxane is entangled and apparently has a network structure, so that the film is hardened. However, when the movement of the molecule becomes active due to the thermal vibration, the phenylsilsesquioxane is released and becomes fluid.
  • the metal foil with a dried film sent from the drying unit is heat-treated in the heat treatment unit.
  • the heat treatment has the following two purposes. (1) melt-softening (ie, reflow) the phenylsilsesquioxane forming the dried film to flatten the surface of the film; (2) proceeding with crosslinking of the polymer following reflow to form a three-dimensional network structure And curing the film.
  • Reflow is a temperature range higher than the synthesis temperature of phenylsilsesquioxane by distillation under reduced pressure, and occurs within a temperature range lower than the temperature at which the dry film begins to cure due to the progress of three-dimensional crosslinking. It is. It is not necessary to employ a special heat treatment process for reflow. When the heat treatment temperature is in the range of 300 ° C. to 450 ° C., reflow occurs in the process of raising the temperature to the heat treatment temperature, and film curing by crosslinking proceeds.
  • Cooling after heat treatment may be performed by blowing cool air from a cooling body.
  • the metal foil with the hardened film is sprayed from both sides, but may be sprayed from one side of the hardened film side.
  • the temperature of the cold air may be room temperature (for example, 25 ° C.).
  • a protective film may be stuck on the flattening film surface to protect the flattening film, and an interleaf paper is inserted to prevent scratches. May be.
  • the drying and the heat treatment are performed continuously, but the drying and the heat treatment may be performed independently. For example, after winding the metal foil with the dry film into a coil, only the heat treatment may be performed again to cure the dry film. In this case, two types of equipment, a drying treatment equipment and a heat treatment equipment, are installed. When the drying and the heat treatment are performed independently, there is an advantage that each processing can be set to an optimum passing speed.
  • Examples 1 to 8 Comparative Examples 1 to 5> The mixing ratio and the manufacturing conditions of each example were carried out according to the conditions described in Table 1. First, using a 1 L flask, the ingredients were blended so as to have the blending ratio shown in Table 1, and the raw materials were blended so that the total amount was 0.7 L. After the preparation, the raw materials were stirred and mixed with a magnetic stirrer for 15 minutes, and refluxed at 80 ° C. for 3 hours under a nitrogen stream to promote hydrolysis. The results of the visual observation in the flask after the reflux are described in the column of “Properties of Hydrolyzed Solution”.
  • the temperature of the oil bath was set to 80 ° C., and the solvent was distilled off under reduced pressure to obtain a condensation reaction product. Thereafter, an organic solvent immiscible with water was added in an amount equivalent to the weight of the condensation reaction product to dissolve the condensation reaction product. At this point, the condensation reaction product is dissolved at a solid concentration of 50% by mass.
  • the 1 L flask was connected to a reflux condenser equipped with a Dean-Stark trap, and heated to reflux. Table 1 shows the set temperature of the oil bath and the reflux time during heating and reflux.
  • the yield was determined from the theoretical amount when the obtained filtrate and the raw material phenyltrialkoxysilane were subjected to a 100% condensation reaction and dissolved in the coating solution. The results are shown in the column of "Yield at 30% dilution". The yield was rated A (very good) for 93% or more, B (good) for less than 85% and less than 85%, and C (bad) for less than 85%. Further, 29 Si NMR and 13 C NMR measurements were performed on the coating solution, and the ratio of the alkoxy group to the total bond of Si and the ratio of the alcohol to Si (mol%) were determined by the above-described methods.
  • Comparative Examples 6 and 7 were carried out in accordance with the conditions shown in Table 1 with respect to the mixing ratio and the production conditions of each example.
  • Comparative Example 6 is an example synthesized according to Patent Document 3.
  • Comparative Example 7 is an example in which the amount of water is increased based on the process of Patent Document 3. In Comparative Example 7, when only water was increased, turbidity was likely to be generated during hydrolysis. Therefore, ethanol was also added so as to easily occur after uniform hydrolysis. First, using a 1 L flask, each component was blended so as to have a blend ratio shown in Table 1, and raw materials were blended so that the total amount was 0.7 L.
  • the obtained coating solution was spin-coated on a stainless steel foil through a filter having a pore size of 0.5 ⁇ m.
  • SUS304MW milk white finish
  • 150 mm ⁇ 150 mm ⁇ 0.05 mm manufactured by Nippon Steel Chemical & Materials Co., Ltd. was used.
  • the number of revolutions of the spin coater was set so that the film thickness became 3.0 ⁇ m.
  • drying was performed in an oven at 80 ° C. for 1 minute, and then heat treatment was performed in a heat treatment furnace at 400 ° C. for 10 minutes to obtain a stainless steel foil with a flattening film in each example.
  • the initial state of the light emitting surface was observed with an optical microscope in a state where 4.5 V was applied to the element to emit light.
  • the device was stored in a thermo-hygrostat at 60 ° C. and a relative humidity of 90% RH for 40 hours, then 4.5 V was applied again to observe the light emitting surface, and the shrinkage width of the light emitting surface from the cathode side was measured. .
  • the shrinkage width exceeded 50 ⁇ m, it was determined as C (impossible), when it was 50 ⁇ m or less, B (good), and when it was 20 ⁇ m or less, it was determined as A (very good). Those having cracks on the substrate are excluded from the evaluation because there is no point in performing element evaluation. The results are described in the column of “Shrinkage width after storage at 60 ° C. and 90% RH for 40 hours”.
  • Table 1 The overall evaluation in Table 1 was based on the following criteria. A: Yield, shrinkage width, and applicability are all judged as A. B: At least one of yield, shrinkage width, and applicability is judged as B, and the rest is judged as A. C: Yield, shrinkage width, One or more of the applicability could not be evaluated or evaluated as C
  • the coating liquid of Comparative Example 3 had an acid catalyst and water was added in a sufficient amount, but the condensation reaction did not proceed sufficiently because no organotin was added. For this reason, the molecular weight of the condensation reaction product was small, and the viscosity at the time of 30 mass% dilution was very low. A rapid dehydration-condensation reaction occurred in the heat treatment step after the spin coating, causing a large volume shrinkage, thereby causing cracks in the film and making it impossible to prototype the device. Since a sound film could not be obtained, the applicability could not be evaluated.
  • the coating solution of Comparative Example 7 was subjected to hydrolysis by increasing the amount of water compared to the coating solution of Comparative Example 6, but after evaporating under reduced pressure at 180 ° C., it was tried to dissolve in toluene. A large amount of insolubles was generated, and the liquid became cloudy. It is presumed that when a large amount of water was added and distilled off under reduced pressure at a high temperature, more random condensates were insoluble in toluene than in the ladder polymer. More than half of the distillate under reduced pressure did not dissolve and could not be filtered under reduced pressure due to clogging, and the coating liquid and the film could not be evaluated.

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Abstract

La présente invention concerne un liquide d'application filmogène planarisé qui contient du phénylsilsesquioxane qui est soluble dans un solvant organique, le liquide d'application filmogène planarisé ayant une viscosité de 2,5 à 35 mPa·s lorsque la concentration en solides du phénylsilsesquioxane est de 30 % en masse, et la proportion de groupes alcoxy liés au Si dans le phénylsilsesquioxane étant de 0 à 5 % par rapport au Si.
PCT/JP2019/038250 2018-09-27 2019-09-27 Liquide d'application filmogène planarisé, procédé de production de liquide d'application filmogène planarisé, feuille métallique pourvue d'un film planarisé, procédé de production d'une feuille métallique pourvue d'un film planarisé WO2020067467A1 (fr)

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JP7473813B2 (ja) 2020-10-02 2024-04-24 日本製鉄株式会社 膜付き金属箔、及び膜付き金属箔の製造方法

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JP2012140528A (ja) * 2010-12-28 2012-07-26 Nippon Steel Materials Co Ltd 皮膜形成用無溶媒塗布液、その塗布液及び皮膜の製造方法
WO2016076399A1 (fr) * 2014-11-12 2016-05-19 新日鉄住金マテリアルズ株式会社 Liquide de revêtement permettant la formation de film de nivellement, et bobine de feuille métallique pourvue du film de nivellement
JP2017155309A (ja) * 2016-03-03 2017-09-07 新日鉄住金マテリアルズ株式会社 膜付きステンレス箔およびその製造方法
JP2018062582A (ja) * 2016-10-13 2018-04-19 新日鉄住金マテリアルズ株式会社 皮膜形成用塗布液の粘度調整方法
JP2018123192A (ja) * 2017-01-30 2018-08-09 新日鉄住金マテリアルズ株式会社 被膜形成用塗布液の製造方法

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Publication number Priority date Publication date Assignee Title
JP2012140528A (ja) * 2010-12-28 2012-07-26 Nippon Steel Materials Co Ltd 皮膜形成用無溶媒塗布液、その塗布液及び皮膜の製造方法
WO2016076399A1 (fr) * 2014-11-12 2016-05-19 新日鉄住金マテリアルズ株式会社 Liquide de revêtement permettant la formation de film de nivellement, et bobine de feuille métallique pourvue du film de nivellement
JP2017155309A (ja) * 2016-03-03 2017-09-07 新日鉄住金マテリアルズ株式会社 膜付きステンレス箔およびその製造方法
JP2018062582A (ja) * 2016-10-13 2018-04-19 新日鉄住金マテリアルズ株式会社 皮膜形成用塗布液の粘度調整方法
JP2018123192A (ja) * 2017-01-30 2018-08-09 新日鉄住金マテリアルズ株式会社 被膜形成用塗布液の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7473813B2 (ja) 2020-10-02 2024-04-24 日本製鉄株式会社 膜付き金属箔、及び膜付き金属箔の製造方法

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