JP2017170410A - Method for manufacturing functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film that has an excellent functionality, does not need large-sized vacuum equipment and a coating process and can be manufactured readily at low cost.SOLUTION: A method for manufacturing a functional film includes means of forming a polymer film and a gas barrier layer at the same time, thereby manufacturing an excellent functional film through a further simple process without a need of large-sized vacuum equipment and a coating process.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a functional film, and in particular, a gas barrier film has good gas barrier properties and does not require a step such as a sputtering step using expensive vacuum equipment, and can be produced simply and at low cost. It relates to a manufacturing method.

The functional film is formed by forming various thin film layers on the surface of the polymer film according to the intended function. Such a functional film is used as a film such as a gas barrier film, an optical filter, or an antireflection film in display devices such as liquid crystal displays and organic EL displays, semiconductor devices, and solar cells.

  For example, a gas barrier film is formed by forming a layer composed of a metal or metal oxide that exhibits gas barrier properties against water vapor or the like on the surface of a polymer film. For such a gas barrier layer, a method is disclosed in which a metal oxide film is formed on a polymer film by plasma chemical vapor deposition (Patent Document 1). Also disclosed is a method of forming an inorganic compound film by applying an inorganic precursor compound on a polymer film to form a coating film, and irradiating the coating film with vacuum ultraviolet rays using an excimer lamp. (Patent Document 2).

JP 2011-144438 A JP 2012-116101 A

  However, the plasma-enhanced chemical vapor deposition method disclosed in Patent Document 1 requires a large vacuum facility for forming a film of an inorganic compound. In addition, the production speed of the film formation is slow, and it is difficult to reduce the manufacturing cost. Even in the method disclosed in Patent Document 2, a process of applying vacuum ultraviolet rays is required in addition to a process of applying and drying the polymer film, and therefore, there are problems such as an increase in processes and necessary facilities.

  That is, the subject of this invention is providing the manufacturing method of the functional film which has the outstanding performance, and a large-sized vacuum installation and many processes are unnecessary, and can be manufactured simply and at low cost.

  In order to solve these problems, the present inventor can produce an excellent gas barrier film by a simpler process by forming a polymer film and a functional layer at the same time without requiring a large vacuum facility or special treatment. We have found a method that can be used to complete the invention.

  That is, the present invention is a method for producing a functional film having a metal oxide layer on at least one surface of the film, and after applying a mixture containing a polymer, a solvent, and a metal oxide layer precursor to a support, The present invention relates to a method for producing a functional film, which comprises removing a solvent and curing a metal oxide layer precursor.

  A preferred embodiment relates to the method for producing a functional film described above, wherein the solvent is removed and the metal oxide layer precursor is simultaneously cured.

  A preferred embodiment relates to the above-described method for producing a functional film, wherein the functional film is a gas barrier film.

  A preferred embodiment relates to the method for producing a functional film described above, wherein the metal oxide layer precursor is soluble in a solvent and insoluble in a polymer.

  A preferred embodiment relates to the method for producing a functional film described above, wherein the metal oxide layer precursor is at least one of a polysilazane compound, a metal alkoxide, a metal salt, or a metal complex.

  A preferred embodiment relates to the above-described method for producing a functional film, wherein the polymer contains at least one of polyimide and polyamic acid.

  According to the method for producing a functional film of the present invention, the process can be simplified by forming the functional layer simultaneously with the formation of the polymer film. In addition, a vacuum device or a coating device is not necessary. By these, the functional film which expresses the outstanding performance with a simple manufacturing process is obtained.

  Embodiments of the present invention will be described below. However, this invention is not limited to this, It can implement in the aspect which added the various deformation | transformation within the described range.

  Unless otherwise specified in the present specification, “A to B” representing a numerical range means “A or more (including A and greater than A)” and “B or less (including B and less than B)”.

  The method for producing a functional film of the present invention comprises: applying a mixture containing a polymer, a solvent, and a metal oxide layer precursor to a support; then removing the solvent and curing the metal oxide layer precursor; This is a method for producing a functional film having a metal oxide layer on at least one surface thereof.

<Functional film>
The functional film in the present invention is not particularly limited as long as it can improve the function of the film serving as the base material. For example, functionalities such as a gas barrier film and a hard coat film can be exemplified.

<Polymer>
The polymer contained in the film used in the production method of the present invention is not particularly limited, and examples thereof include a thermoplastic polymer, a thermosetting polymer, and a photocurable polymer. More specifically, various polymers such as a cycloolefin polymer, polycarbonate, polyester, polyamide, polyimide, polyamide-imide, or polyester-imide can be exemplified. Any one of these polymers may be used alone, or a mixture of two or more different polymers may be used. Among these, polyimide having high heat resistance and high strength is particularly preferable.

  Polyimide is obtained using polyamic acid as a precursor. The polyamic acid is obtained by reacting an aromatic diamine (hereinafter also referred to as diamine) and an aromatic dianhydride (hereinafter also referred to as acid dianhydride). More specifically, usually, the aromatic diamine and the aromatic dianhydride are dissolved in an organic solvent so as to have a substantially equimolar amount, and the resulting solution is subjected to controlled temperature conditions. Under stirring until the polymerization of acid dianhydride and diamine is complete. The solution containing the polyamic acid thus obtained is usually obtained at a concentration of 5 wt% to 35 wt%, more preferably 10 wt% to 30 wt%. When the concentration is in this range, an appropriate molecular weight and solution viscosity are obtained, and a polymer solution that can be easily formed into a film or the like can be obtained.

  The aromatic diamine is not particularly limited. For example, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2-bis {4- (4 -Aminophenoxy) phenyl} propane, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, bis {4- (3-aminophenoxy) phenyl} sulfone, bis {4- (4-amino Phenoxy) phenyl} sulfone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3′- Diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dichlorobenzidine, 3,3'-dimethyl Rubenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine) ), 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(1,4-phenylenebis (1-methylethylidene) )) Bisaniline, 4,4 ′-(1,3-phenylenebis (1-methylethylidene)) bisaniline, 4,4′-diaminobenzanilide, or a combination of two or more of these.

  The aromatic dianhydride is not particularly limited, and for example, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic Acid dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxyphthalic dianhydride, ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid) Anhydride), pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4 4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane Carboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4′-hexafluoro Isopropylidene diphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenebis (tri Merit acid monoester anhydride), aromatic tetracarboxylic dianhydride such as p-phenylenediphthalic anhydride, or a combination of two or more of these.

  The aromatic diamine and the aromatic dianhydride may be reacted so as to have a substantially equimolar amount, and the order of addition, the combination of monomers, and the composition are not particularly limited.

  The organic solvent used as the polymerization solvent for producing the polyamic acid is not particularly limited as long as it dissolves the aromatic diamine component, the aromatic dianhydride component, and the resulting polyamic acid. . If, for example, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide or the like is used as a polymerization solvent, the resulting polyamic acid solution is used as it is as a film. It can be set as the polyamic acid solution (varnish) used for chemical conversion.

  The reaction temperature for producing the polyamic acid is not particularly limited, but is preferably −10 ° C. to + 50 ° C. Within such a range, the reaction proceeds at a good reaction rate and is excellent in productivity, which is preferable. The reaction time is not particularly limited, but is usually from several minutes to several hours.

  Polyimide is a polymer imidized by heat treatment (also referred to as a thermal cure method) or a heat treatment (also referred to as a chemical cure method) by mixing polyamic acid with a curing agent. The curing agent is intended to include a dehydrating agent and a catalyst. Here, the dehydrating agent is not particularly limited as long as it is a dehydrating ring-closing agent for polyamic acid. For example, aliphatic acid anhydride, aromatic acid anhydride, N, N′-dialkylcarbodiimide, lower aliphatic Listed are halides, halogenated lower aliphatic acid anhydrides, aryl sulfonic acid dihalides, thionyl halides, and the like. These may be used alone or in appropriate combination of two or more. Among these, aliphatic acid anhydrides or aromatic acid anhydrides can be particularly preferably used.

  The catalyst is not particularly limited as long as it is a component having an effect of promoting the dehydrating and ring-closing action of the dehydrating agent on the polyamic acid. Specifically, for example, an aliphatic tertiary amine, an aromatic tertiary amine, and the like. And heterocyclic tertiary amines. Among these, for example, nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, isoquinoline, quinoline, diethylpyridine, and β-picoline are particularly preferably used.

<Solvent>
The solvent used in the production method of the present invention may be any solvent as long as it can dissolve the polymer and the gas barrier substance precursor, and can be appropriately selected according to the polymer to be used and the gas barrier substance precursor. Specifically, for example, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, phenols such as phenol and p-chlorophenol, methanol , Alcohols such as ethanol, aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene, acetone, ethyl acetate, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene Glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl cellosolve, Use tilselsolve, 2-pyrrolidone, N-methyl-2-pyrrolidone, pyridine, triethylamine, dimethylformamide, dimethylacetamide, acetonitrile, butyronitrile, methyl isobutyl ketone, methyl ether ketone, cyclohexane, cyclopentanone, carbon disulfide, water, etc. be able to. These solvents can be used alone or in combination of two or more.

<Metal oxide layer precursor>
The metal oxide layer precursor used in the production method of the present invention is not particularly limited as long as it reacts with oxygen, water, etc. by applying energy such as heat and light, and changes into a metal oxide layer. And can be appropriately selected according to the target functionality. Specifically, for example, polysilazane compounds, metal alkoxides, metal salts, organometallic complexes, and the like can be used. These gas barrier substance precursors can be used alone or in combination of two or more.

  The metal oxide precursor of the present invention is preferably soluble in a solvent and insoluble in a polymer. The metal oxide precursor being soluble in a solvent means a state in which the metal oxide precursor is solvated in the solvent. In addition, that the metal oxide precursor is insoluble in the polymer refers to a state where the polymer molecule and the metal oxide precursor are not solvated.

A polysilazane compound reacts with a substance having a hydroxyl group to produce silicon dioxide. For example, in the general formula (SiR ⁴ R ⁵ NR ⁶ ) (wherein R ^{4 to} R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a substituted hydrocarbon group having 1 to 8 carbon atoms). Among them, perhydropolysilazane represented by the general formula (SiH ₂ NH) is preferable. The polysilazane compound is easily available because it is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product or the like can be used as it is as a coating solution for forming a gas barrier layer containing a gas barrier substance precursor. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.

A metal alkoxide is a compound in which a hydrogen atom of an alcohol (R—OH) is substituted with a metal. For example, the general formula _{^{(R 1) n-x -M-}} (OR 2) x ( provided that ^R 1, ^{R 2} are each independently an organic group having 1 to 8 carbon atoms, M is a metal atom .x 2-4 And n is 2 to 4). Examples of metal atoms include Si, Ti, Al, and Zr.

Metal M is Si as the _{^{(R 1) n-x -Si-}} (OR 2) x, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Examples thereof include dimethyldimethoxysilane and dimethyldiethoxysilane.

Examples of (R ¹ ) _n -x-Zr- (OR ² ) _x in which the metal M is Zr include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.
Metal M is Ti as the _{^{(R 1) n-x -Ti-}} (OR 2) x, can be exemplified tetramethoxysilane titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium and the like.

Metal M is Al as the _{^{(R 1) n-x -Al-}} (OR 2) x, can be exemplified tetramethoxysilane aluminum, tetraethoxy aluminum, tetraisopropoxy aluminum, tetrabutoxy aluminum.

  These metal alkoxides can be used alone or in combination of two or more.

  A metal salt is a compound in which a metal cation and an anion are ion-bonded. For example, metal nitrates, sulfates, phosphates, carbonates, acetates, oxalates and the like can be mentioned. More specifically, any metal salt capable of forming an oxide, nitride or oxynitride by applying energy such as heat and light can be used in the present invention without any particular limitation. Although it does not restrict | limit especially as a metal element which comprises these metal salts, It is preferable that at least 1 type selected from the group which consists of Al, Ti, and Si is included. Of the metal salts, nitrate is particularly preferable. Nitrate has a low decomposition temperature, and oxide formation proceeds simultaneously with the desorption process of crystal water without passing through hydroxide.

  Examples of the organometallic complex include β-diketone complexes such as an acetylacetone complex. In these acetylacetone complexes, a trifluoropropyl group may be introduced instead of the terminal methyl group. These various organometallic complexes can be used alone or in combination of two or more.

<Manufacture of functional film>
Regarding the production method of the present invention, for example, a mixed solution of a polymer, a solvent and a metal oxide layer precursor is preferably cast on the surface of a support (for example, a metal, ceramic, polymer roll or belt) Forms a polymer solution film containing a metal oxide layer precursor having a uniform thickness of about 10 μm to 2000 μm, particularly preferably about 20 μm to 1000 μm. Subsequently, it heats using heat sources, such as a hot air and infrared rays, and a functional film is formed by performing removal of a solvent, and hardening of a metal oxide layer precursor simultaneously. In this case, curing may be performed by irradiating ultraviolet rays or the like instead of heating. Moreover, it is desirable that the functional film is long.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by an Example.

(Water vapor permeability measurement)
In order to evaluate the gas barrier properties of the film, the water vapor permeability was measured. For measurement, DELTAPERRM (manufactured by TECHNOLOX) was used, and the water vapor transmission rate was measured under conditions of an atmospheric temperature of 40 ° C. and a humidity of 90%. Since the upper limit of measurement of this apparatus is 10 g / m ² / day, a value higher than that is expressed as OVER.

(Synthesis Example 1)
Polymerized in N, N-dimethylformamide (DMF) so that the molar ratio of pyromellitic dianhydride, 4,4′-diaminodiphenyl ether, and p-phenylenediamine is 4/3/1. An acid solution was obtained.

Example 1
A polysilazane solution (NN110-20: non-catalytic xylene solvent 20% manufactured by Merck Performance Materials LLC) was added to the polyamic acid solution prepared in Synthesis Example 1 as a curing agent composed of acetic anhydride, isoquinoline and DMF, and a metal oxide layer precursor. Concentration product) was mixed to obtain a mixed resin solution, which was applied onto the aluminum foil using a comma coater. Thereafter, it was dried at 110 ° C. for 75 seconds to obtain a gel film having self-supporting properties. After this gel film was peeled off from the aluminum foil, both ends of the film were held with pins and heat-treated in a furnace. The first heat treatment was dried at 275 ° C. × 25 seconds to obtain a gas barrier polyimide film having a thickness of 12.5 μm. The results of measuring the water vapor permeability of the obtained film are shown in Table 1.

(Example 2)
A gas barrier polyimide film was obtained in the same manner as in Example 1 except that tetraethoxysilane (manufactured by Wako Pure Chemical Industries) was mixed as the metal oxide layer precursor. The results of measuring the water vapor permeability of the obtained film are shown in Table 1.

(Comparative Example 1)
A polyimide film was obtained in the same manner as in Example 1 except that the metal oxide layer precursor was not applied. The results of measuring the water vapor permeability of the obtained film are shown in Table 1.

  As can be seen from the comparison between Example 1 and Comparative Example 1 and Example 2 and Comparative Example 1, it can be seen that an excellent functional film can be produced because the gas barrier property is improved by an easy process.

Claims (6)

  A method for producing a functional film having a metal oxide layer on at least one surface of a film, wherein a mixture containing a polymer, a solvent, and a metal oxide layer precursor is applied to a support, and then the solvent is removed and the metal is oxidized. A method for producing a functional film, comprising curing a physical layer precursor.   The method for producing a functional film according to claim 1, wherein the solvent is removed and the metal oxide layer precursor is simultaneously cured.   The method for producing a functional film according to claim 1, wherein the functional film is a gas barrier film.   The method for producing a functional film according to any one of claims 1 to 3, wherein the metal oxide layer precursor is soluble in a solvent and insoluble in a polymer.   The functional film according to any one of claims 1 to 4, wherein the metal oxide layer precursor is at least any one of a polysilazane compound, a metal alkoxide, a metal salt, or a metal complex. Production method.   The method for producing a functional film according to claim 1, wherein the polymer contains at least one of polyimide and polyamic acid.