JP2015193797A - transparent resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent resin film excellent in flexibility and gas barrier properties.SOLUTION: The transparent resin film of the present invention is formed by applying a coating liquid which contains: a resin solution obtained by dissolving a predetermined resin compound in a highly polar solvent having a dielectric constant of 10 or more; and an organic-treated layered silicate. In one embodiment, the transparent resin film of the present invention has a light transmittance at a wavelength of 550 nm of 70% or more. In one embodiment, the transparent resin film of the present invention has a haze value of 10% or less.

Description

  The present invention relates to a transparent resin film.

  In recent years, with the development of video communication technology, display devices such as flat panel displays (FPDs: for example, liquid crystal display devices and organic EL display devices) are becoming lighter and thinner. Conventionally, a glass substrate is often used as a substrate of a display device. A glass substrate is excellent in transparency, solvent resistance, gas barrier properties, and heat resistance, but is difficult to reduce in weight due to fragility. Therefore, it has been studied to use a resin film instead of glass. The substrate is required to have high gas barrier properties (for example, water vapor barrier properties). Moreover, since the manufacturing process of a display element includes the process process under high temperature, a high heat resistance is calculated | required by the board | substrate. That is, a resin film excellent in gas barrier properties and heat resistance is required as a resin film used for a substrate.

JP 2007-63118 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a transparent resin film excellent in gas barrier properties and heat resistance.

The transparent resin film of the present invention is formed by applying a coating solution containing a highly polar solvent, a resin compound dissolved in the highly polar solvent, and an organically treated layered silicate, The relative dielectric constant of the highly polar solvent is 10 or more, and the content ratio of the organically treated layered silicate is 1 to 30 parts by weight with respect to 100 parts by weight of the resin compound.
In one embodiment, the transparent resin film of the present invention has a light transmittance of 70% or more at a wavelength of 550 nm.
In one embodiment, the transparent resin film of the present invention has a haze value of 10% or less.
In one embodiment, the transparent resin film of the present invention has an elastic modulus at 25 ° C. of 1.5 GPa to 10 GPa.
In one embodiment, the transparent resin film of the present invention, fracture toughness value at 25 ° C. ^is a ^{1.5MPa · m 1/2 ~10MPa · m 1/2} .
In one embodiment, the transparent resin film of the present invention contains water and a mixed solvent containing N-methylpyrrolidone and / or dimethyl sulfoxide and having a water content of 5% by weight or more. Solvent cracks do not occur.
In one embodiment, the organically treated layered silicate is subjected to an organic treatment using a quaternary imidazolium salt and / or a quaternary phosphonium salt as an organic treatment agent.
In one embodiment, the glass transition temperature of the said resin compound is 180 degreeC-450 degreeC.
In one embodiment, the weight average molecular weight of the resin compound is 2 × 10 ^{4 to} 100 × 10 ⁴ in terms of polystyrene.
In one embodiment, the resin compound has a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2):
In Formula (1), R ¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, R ² is a linear or branched alkyl group having 2 to 5 carbon atoms, and A ¹ And A ² are each independently at least one selected from the linking groups represented by the above general formulas (3) to (7), X ¹ is an arylene group, and X ¹ is a para- or meta- position in linked to the linking group ^{a 2} and the linking group ^{a 1} or ^{a 3,} in formula (2), ^{R 3} is a methyl group or an aryl group, ^{a 3} and ^{a 4} are each independently the general formula It is at least one selected from the linking groups represented by (3) to (7), X ² is an arylene group, and X ² is a linking group A ⁴ and a linking group A ^{1 in} the para or meta position. connected to and a ^3.
In one embodiment, in the resin compound, the total number of X ¹ and X ² having a linking group at the para position is 3 times the total number of X ¹ and X ² having a linking group at the meta position. That's it.
In one embodiment, in the resin compound, R ¹ is a methyl group, R ² is an isobutyl group, R ³ is a methyl group or an aryl group, and A ¹ , A ² , A ³ and A ⁴ Are each independently a linking group represented by the general formula (3) or (4), and X ¹ is an aryl group linked to the linking group A ² and the linking group A ¹ or A ^{3 in the} para position. , X ² is an aryl group linked to the linking group A ⁴ and the linking group A ¹ or A ^{3 in the} para position.
In one embodiment, the said resin compound further has a repeating unit represented by General formula (8):
In formula (8), R ⁴ and R ⁵ are each independently a methyl group or hydrogen, and B is a substituted or unsubstituted cycloalkane having 4 to 9 carbon atoms, or substituted or unsubstituted fluorene.
According to another aspect of the present invention, a transparent substrate is provided. The transparent substrate includes an inorganic glass having a thickness of 100 μm or less and the transparent resin film disposed on one side or both sides of the inorganic glass.
In one embodiment, the transparent substrate of the present invention has a layer thickness of 150 μm or less.
In one embodiment, the fracture diameter when the transparent substrate is bent and bent is 50 mm or less.
According to still another aspect of the present invention, a display element is provided. This display element is manufactured using the transparent substrate.
According to still another aspect of the present invention, a solar cell is provided. This solar cell is produced using the transparent substrate.
According to still another aspect of the present invention, an illumination element is provided. This illumination element is manufactured using the transparent substrate.

  According to the present invention, a coating solution prepared using a highly polar solvent and containing a resin compound soluble in the highly polar solvent and an organically treated layered silicate is used, and the coating solution is applied. By forming a film, a transparent resin film having excellent gas barrier properties and heat resistance can be provided.

(A) is a schematic sectional drawing of the transparent substrate by one Embodiment of this invention. (B) is a schematic sectional drawing of the transparent substrate by another embodiment of this invention. (C) is a schematic sectional drawing of the transparent substrate by another embodiment of this invention. It is a graph which shows the storage stability of the transparent resin film obtained in Example 1 and Comparative Example 1. 2 is a TEM photograph showing a cross section of the transparent resin film obtained in Example 1. FIG.

A. Transparent resin film The transparent resin film of the present invention comprises a resin solution obtained by dissolving a predetermined resin compound (resin compound soluble in the high polarity solvent) in a high polarity solvent having a relative dielectric constant of 10 or more, and an organic resin. It is formed by applying a coating liquid containing a layered silicate that has been subjected to a chemical treatment. The transparent resin film thus formed contains the above resin compound and an organically treated layered silicate, and the transparent resin film is excellent in gas barrier properties and heat resistance. Moreover, by forming using a highly polar solvent, the dispersibility of the organically treated layered silicate is good, and a transparent resin film excellent in transparency, gas barrier properties and toughness can be obtained.

A-1. Resin Compound As the resin compound, any appropriate resin compound can be used as long as the effects of the present invention are obtained. As described above, in the present invention, a resin compound soluble in a highly polar solvent having a relative dielectric constant of 10 or more is used as the resin compound. In the present specification, “soluble” means that it can be dissolved in a predetermined solvent at a concentration of 10% by weight or more at 25 ° C.

  The resin film of this invention has the said resin compound as a main component. The content ratio of the resin compound is preferably 50% to 99% by weight, more preferably 75% to 99% by weight, and still more preferably 80% to 97% by weight with respect to the weight of the resin film. %, Particularly preferably 85% to 95% by weight.

As the resin compound constituting the transparent resin film of the present invention, a resin compound having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) is preferably used. By including such a resin compound, a transparent resin film having excellent toughness can be obtained. When a transparent substrate is formed by combining such a transparent resin film and a thin inorganic glass, it is possible to obtain a transparent substrate in which cracks hardly develop during cutting. Moreover, the transparent resin film excellent in solvent crack resistance can be obtained.
In formula (1), R ¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably Is a methyl group. R ² is a linear or branched alkyl group having 2 to 5 carbon atoms, preferably a linear or branched alkyl group having 3 or 4 carbon atoms, and more preferably an isobutyl group. . A ¹ and A ² are each independently at least one selected from the linking groups represented by the general formulas (3) to (7), preferably represented by the general formula (3) or (4). It is a linking group. X ¹ is an arylene group, preferably a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and more preferably a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. X ¹ is linked to the linking group A ² and the linking group A ¹ or A ³ at the para or meta position.
In Formula (2), R ³ is a methyl group or an aryl group, preferably a methyl group or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a methyl group or 6 to 12 carbon atoms. A substituted or unsubstituted aryl group. A ³ and A ⁴ are each independently at least one selected from the linking groups represented by the general formulas (3) to (7), preferably represented by the general formula (3) or (4). A linking group. X ² is an arylene group, preferably a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and more preferably a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. X ² is linked to the linking group A ⁴ and the linking group A ¹ or A ³ at the para or meta position.
Specific examples of X ¹ and X ² include a benzene ring, a naphthalene ring, and a biphenyl ring.

In the general formula (1) and a resin compound having a repeating unit represented by (2), the total number of X ¹ and X ² having a linking group at the para position, X ¹ and X ² having a linking group in the meta position Is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 9 times or more. Most preferably, A ^{1 to} A ⁴ bind only to the para positions of X ¹ and X ² . If a resin compound having a repeating unit having such a structure is used, a transparent resin film having excellent solvent crack resistance can be obtained.

  The molar ratio of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) (general formula (2) / general formula (1)) is preferably 0.5 to 2. 0.0, more preferably 0.7 to 1.6.

Preferably, the resin compound further has a repeating unit represented by the following general formula (8). If the said resin compound has such a repeating unit, the transparent resin film excellent in heat resistance can be obtained.
In formula (8), R ⁴ and R ⁵ are preferably each independently a methyl group or hydrogen. B is preferably a substituted or unsubstituted cycloalkane or substituted or unsubstituted fluorene having 4 to 9 carbon atoms, and more preferably a substituted or unsubstituted cycloalkane or substituted or unsubstituted fluorene having 6 to 9 carbon atoms. Fluorene.

  The ratio of the repeating unit represented by the general formula (8) is preferably 30 mol% or less with respect to the total number of moles of the repeating unit represented by the general formula (1) or (2). Preferably it is 3 mol%-30 mol%, Most preferably, it is 5 mol%-20 mol%.

  Examples of the resin compound include (a) 4 ′-(1,3-dimethylbutylidene) bisphenol, 2,2-bis (4-hydroxyphenyl) -4-methyl-pentane, and 3,3-bis (4- At least one selected from the group consisting of (hydroxyphenyl) pentane and 2,2-bis (4′-hydroxyphenyl) hexane, (b) 4,4 ′-(1-phenylethylidene) bisphenol, 4,4′- (C) at least one selected from the group consisting of (1-phenylpropylidene) bisphenol, 4,4 ′-(1-phenylpentylidene) bisphenol and 4,4 ′-(1-phenylhexylidene) bisphenol; Consists of terephthalic acid chloride, isophthalic acid chloride, phthalic acid chloride and biphenyl dicarboxylic acid chloride Monomer composition containing at least one selected from the can be obtained by copolymerization with any suitable polymerization method. When the resin compound has a repeating unit represented by the general formula (8), the monomer composition may further include, for example, bisphenols having a fluorene group, bisphenols having a cyclohexane group, and the like. Specific examples of the bisphenol having a fluorene group include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Specific examples of the bisphenol having a cyclohexane group include 4,4 '-(3,3,5-trimethylcyclohexylidene) bisphenol.

  The polymerization degree of the resin compound constituting the transparent resin film of the present invention is preferably 10 to 6000, more preferably 20 to 5000, and particularly preferably 50 to 4000.

The weight average molecular weight of the resin compound constituting the transparent resin film of the present invention (value measured by gel permeation chromatography (solvent: THF) using a standard polystyrene calibration curve) is preferably 2 × in terms of polystyrene. 10 ^{4 to} 100 × 10 ⁴ , more preferably 8 × 10 ^{4 to} 100 × 10 ⁴ , still more preferably 9 × 10 ⁴ to 50 × 10 ⁴ , and particularly preferably 10 × 10 ⁴ to 30 ×. 10 is ^four. When the weight average molecular weight of the resin compound is smaller than 2 × 10 ⁴ , the solvent crack resistance may be insufficient. If it is larger than 100 × 10 ⁴ , the viscosity may be too high and handling may be difficult.

  The glass transition temperature of the resin compound constituting the transparent resin film of the present invention is preferably 180 ° C. to 450 ° C., more preferably 180 ° C. to 350 ° C., further preferably 230 ° C. to 330 ° C., particularly Preferably it is 250 degreeC-300 degreeC, Most preferably, it is 260 degreeC-300 degreeC. If it is such a range, it is excellent in heat resistance and can obtain the transparent resin film which is hard to color.

  As the resin compound constituting the transparent resin film of the present invention, when a layer having a thickness of 30 μm is formed using only the resin compound, the total light transmittance of the layer is preferably 70% or more, more preferably 80%. More preferably, a resin compound of 85% or more, most preferably 88% or more can be used. In addition, when a layer having a thickness of 30 μm is formed using only the resin compound, a resin compound in which the b value in the hunter color system of the layer is 1.5 or less can be preferably used.

A-2. Organically treated layered silicate The transparent resin film of the present invention contains an organically treated layered silicate. Specifically, the organic treatment is a treatment for adding heat resistance to the layered silicate. Details will be described later. In the present specification, the organically treated layered silicate is also referred to as an organically treated layered silicate. Moreover, the layered silicate before the organic treatment is simply referred to as a layered silicate.

  The layered silicate is, for example, a plate-like crystal composed of two layers of silica tetrahedron and a magnesium octahedron layer or aluminum octahedron layer existing between two layers of silica tetrahedron (for example, (Thickness 1 nm) has a laminated structure in which several hundred to several thousand sheets are laminated.

  Examples of the layered silicate include smectite, bentonite, montmorillonite, and kaolinite. A commercial product may be used as the layered silicate. Specific examples of commercially available layered silicates include trade name “Synthetic Smectite SWF” manufactured by Coop Chemical Co., Ltd. and trade name “Purified Bentonite Kunipia F” manufactured by Kunimine.

  The thickness of the layered silicate is preferably 0.5 nm to 30 nm, more preferably 0.8 nm to 10 nm. The length of the long side of the layered silicate is preferably 50 nm to 1000 nm, more preferably 300 nm to 600 nm. The long side of the layered silicate means the longest side among the sides constituting the layered silicate.

  The aspect ratio of the layered silicate (ratio L / T between the thickness T and the long side length L) is preferably 25 or more, and more preferably 200 or more. By using a layered silicate having a high aspect ratio, a transparent resin film having a high gas barrier property can be obtained even if the amount of layered silicate added is small. Further, if the amount of layered silicate added is small, a transparent resin film having high transparency and excellent flexibility can be obtained. The upper limit of the aspect ratio of the layered silicate is usually 300.

  In one embodiment, it is obtained by appropriately organically treating a layered silicate, and does not color even at a temperature of 200 ° C. or higher (preferably 230 ° C. or higher, more preferably 230 ° C. to 400 ° C.). Treated layered silicate is used. Preferably, an organically treated layered silicate that is not colored even when heated at 230 ° C. for 10 minutes is used. In the present specification, “not colored” means that the organically treated layered silicate is not colored by visual confirmation. Further, whether or not the organically treated layered silicate is colored can also be determined by measuring the transmission color of the transparent resin film. Specifically, when a film is composed of a resin compound alone, a resin compound having a b value of 2 or less in the hunter color system of the film is used, and the layered silicate 10 is added to 100 parts by weight of the resin compound. When the b value of the transparent resin film containing parts by weight is 2 or less, it can be said that the layered silicate is not colored.

The organic treatment is performed by using an inorganic cation (for example, Na ⁺ , Ca ²⁺ , Al ³⁺ , Mg ²⁺ ) originally present between the plate crystals in the layered silicate using an appropriate salt as an organic treatment agent. This is performed by cation exchange. As the organic treatment agent used for the cation exchange, any appropriate salt can be used as long as the effect of the present invention is obtained. For example, a nitrogen-containing heterocyclic quaternary ammonium salt, a quaternary phosphonium salt can be used. Etc. Preferably, quaternary imidazolium salts, triphenylphosphonium salts and the like are used. Layered silicates organically treated with these salts are excellent in heat resistance and do not color even at high temperatures (eg, 200 ° C. or higher). Further, the organically treated layered silicate is excellent in dispersibility in a coating liquid (a highly polar solvent in which the resin compound is dissolved) for forming a transparent resin film. If an organically treated layered silicate with high dispersibility is used, a transparent resin film with high transparency, gas barrier properties and toughness can be formed. More preferably, a quaternary imidazolium salt is used as the organic treatment agent. Since the quaternary imidazolium salt is more excellent in heat resistance, a transparent resin film with less coloring can be obtained even at high temperatures by using a layered silicate organically treated with a quaternary imidazolium salt. .

  Specific examples of quaternary imidazolium salts include 1-decyl-3-methylimidazolium chloride (DMIMCL), 1-hexyl-3-methylimidazolium chloride (HMIMCL), and 1-methyl-3-octylimidazolium chloride. (MOIMCL), 1-methyl-benzimidazolium chloride (MBBIMCL), 1,2-dimethyl-3-hexadecylimidazolium tetrafluoroborate (DMHDIMBF4), 1-decyl-2,3-dimethylimidazolium tetrafluorobo Lat (DDMIMBF4) and the like. Of these, DMIMCL is preferably used because of its excellent dispersibility.

  Specific examples of the triphenylphosphonium salt include 10- [3,5-bis (methoxycarbonyl) phenoxy] decyltriphenylphosphonium bromide (IP10TP), dodecyltriphenylphosphonium bromide (C12TP), and the like.

The counter anion of the salt used as the organic treatment agent is, for example, Cl ⁻ , B ⁻ or Br ⁻ . The counter Ani non is preferably Cl ^- or B ^-, more preferably an Cl ^- is. Such a salt containing a counter ion is excellent in exchangeability with an inorganic cation originally present in the layered silicate.

  The salt used as the organic treatment agent preferably has a long-chain alkyl group. Carbon number of this alkyl group becomes like this. Preferably it is 4 or more, More preferably, it is 6 or more, More preferably, it is 8-12. If a salt having a long chain alkyl group is used, the salt spreads between the plate crystals in the layered silicate, and the interaction between the crystals is weakened. As a result, the organically treated layered silicic acid in the resin compound is reduced. The dispersibility of the salt is improved. If the dispersibility of the organically treated layered silicate is high, a transparent resin film having high transparency and gas barrier properties can be formed.

  The thickness of the organically treated layered silicate is preferably 0.5 nm to 30 nm, more preferably 0.8 nm to 20 nm, and further preferably 1 nm to 5 nm.

  The organically treated layered silicate is obtained, for example, by dispersing a layered silicate and a salt as an organically treating agent in any appropriate solvent (for example, water) and stirring under predetermined conditions. Can do. The addition amount of the salt as the organic treatment agent is preferably 1.1 times or more, more preferably 1.2 times or more, on a molar basis with respect to the cation originally present in the layered silicate. Yes, more preferably 1.5 times or more. Whether or not the layered silicate has been subjected to organic treatment can be confirmed by measuring the interlayer distance of the layered silicate by X-ray diffraction analysis and confirming the spread of the interlayer distance.

  The content of the organically treated layered silicate is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the resin compound in the transparent resin film. More preferably 3 to 15 parts by weight, particularly preferably 5 to 15 parts by weight. Within such a range, it is possible to obtain a transparent resin film that is excellent in gas barrier properties and transparency and is less colored.

A-3. Formation of Transparent Resin Film A transparent resin film of the present invention comprises a coating solution containing a high polarity solvent, a resin compound dissolved in the high polarity solvent, and an organically treated layered silicate dispersed in the high polarity solvent. Can be obtained by coating. More specifically, the transparent resin film of the present invention can be obtained by applying the coating liquid to any appropriate substrate and then drying the coating layer. As the substrate, a substrate formed from a material that does not deteriorate due to the coating liquid can be preferably used. In one embodiment, after forming a transparent resin film on a substrate, the transparent resin film is peeled off. In another embodiment, a laminate comprising a substrate and a transparent resin film is provided without peeling off the transparent resin film. For example, a transparent substrate (described later) composed of inorganic glass and a transparent resin film can be obtained using inorganic glass as a base material.

  The relative dielectric constant of the high polarity solvent is 10 or more, preferably 20 or more, more preferably 30 or more, and particularly preferably 30 to 50. If a solvent having such a high polarity is used, a resin compound having high polarity and excellent heat resistance can be dissolved to prepare a coating liquid, and a transparent resin film having excellent heat resistance can be formed by the coating liquid. Can do. In addition, if a highly polar solvent is used, a coating liquid having excellent dispersibility of the organically treated layered silicate can be prepared, and the coating liquid is excellent in transparency, toughness and gas barrier properties, and has little coloring. A transparent resin film can be formed. In addition, when a solvent (for example, water) having a relative dielectric constant higher than 50 is used, a resin compound that is soluble in the solvent is greatly limited, and a resin film excellent in characteristics such as toughness and solvent crack resistance is obtained. You may not be able to.

  Specific examples of the highly polar solvent include dimethyl sulfoxide, dimethylacetamide, acetone, N-methylpyrrolidone, dimethylformamide, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile and the like. Among them, dimethylacetamide is preferable because it has a high relative dielectric constant and has a boiling point that is easy to handle. In addition, you may use a mixed solvent as a solvent contained in the said coating liquid. In this case, the mixed solvent obtained by mixing two or more solvents needs to be a highly polar solvent. In one embodiment, a solution in which a resin compound is dissolved in a first solvent and an organically treated layered silicate dispersed in a second solvent and a dispersion are mixed, and the coating liquid is Prepared. In this embodiment, both the first solvent and the second solvent are preferably highly polar solvents (that is, solvents having a relative dielectric constant of 10 or more). In this way, the first solvent and the second solvent can be mixed while preventing aggregation of the organically treated layered silicate, and as a result, a transparent resin film having excellent transparency can be obtained. it can. The first solvent and the second solvent may be highly polar solvents prepared using two or more solvents.

  The concentration of the resin compound in the coating solution is preferably 5% by weight or more, more preferably 7% by weight or more, and further preferably 8% by weight to 10% by weight.

  The content ratio of the organically treated layered silicate in the coating solution is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the resin compound. More preferably, it is 5 to 15 parts by weight.

  As an application method of the coating liquid, any appropriate method can be used, for example, air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, Coating methods such as spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, and die coating; relief printing methods such as flexographic printing, intaglio printing methods such as direct gravure printing methods, offset gravure printing methods, and offset printing methods Printing methods such as lithographic printing methods such as stencil printing methods such as screen printing methods.

  Any appropriate drying method (for example, natural drying, air drying, heat drying) may be employed as a method for drying the coating layer formed by applying the coating liquid. For example, in the case of heat drying, the drying temperature is typically 80 ° C. to 150 ° C., and the drying time is typically 1 minute to 30 minutes.

  After drying the coating layer, a heat treatment may be further performed. Any appropriate heat treatment method can be adopted as the heat treatment method. Typically, the heat treatment temperature is 100 ° C. to 250 ° C., and the time is 1 minute to 30 minutes.

  The elastic modulus at 25 ° C. of the transparent resin film of the present invention is preferably 1.5 GPa to 10 GPa, more preferably 1.6 GPa to 9 GPa, and particularly preferably 1.7 GPa to 8 GPa. The transparent resin film having an elastic modulus in the above range relieves local stress in the tearing direction to defects generated during deformation when a transparent substrate is obtained by combining the transparent resin film and inorganic glass. Therefore, even when the inorganic glass is thinned in the transparent substrate, the inorganic glass is less likely to crack and break.

Fracture toughness value at 25 ° C. of the transparent resin film of the present invention is preferably a ^{1.5MPa · m 1/2 ~10MPa · m 1/2} , more preferably ^{2MPa · m 1/2 ~8MPa · m 1} / ^2, particularly preferably ^{2.5MPa · m 1/2 ~6MPa · m 1/2} . If it is such a range, since the said transparent resin film has sufficient tenacity, when a transparent substrate is formed in combination with inorganic glass, the progress and breakage of the crack of this transparent substrate can be prevented.

  The linear expansion coefficient of the transparent resin film of the present invention is preferably 50 ppm / ° C. or less, more preferably 48 ppm / ° C. or less, and particularly preferably 40 ppm / ° C. to 45 ppm / ° C. By including the organically treated layered silicate, the linear expansion coefficient of the transparent resin film can be reduced. When such a transparent resin film and a thin inorganic glass are combined to form a transparent substrate, the inorganic glass can be prevented from being damaged at high temperatures.

  The light transmittance at a wavelength of 550 nm of the transparent resin film of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and most preferably 88% or more. In the present invention, by using a highly polar solvent and forming a transparent resin film by coating, the organically treated layered silicate is well dispersed and a transparent resin film having a high light transmittance can be obtained. .

  The haze value of the transparent resin film of the present invention is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 2% or less. In the present invention, by using a highly polar solvent and forming a transparent resin film by coating, the organically treated layered silicate is well dispersed, and a transparent resin film having a small haze value can be obtained.

  The transparent resin film of this invention has the outstanding durability with respect to the solvent (for example, resist stripping solution) used when manufacturing a display element, a solar cell, or a lighting element. Specifically, the transparent resin film of the present invention contains 20% by weight to 95% by weight of at least one solvent selected from the group consisting of acetone, N-methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide. Solvent cracks do not occur when the mixed solvent is contacted. Preferably, the transparent resin film of the present invention is a mixed solvent containing 70 wt% to 95 wt% of at least one solvent selected from the group consisting of acetone, N-methylpyrrolidone, dimethyl sulfoxide, and N, N-dimethylformamide. Solvent cracks do not occur when contact is made. More preferably, the transparent resin film of the present invention contains 90% by weight to 95% by weight of at least one solvent selected from the group consisting of acetone, N-methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide. Solvent cracks do not occur when contacting the solvent. Examples of solvents other than acetone, N-methylpyrrolidone, dimethyl sulfoxide, and N, N-dimethylformamide contained in the mixed solvent include water, isopropyl alcohol, and the like. More specific examples of the mixed solvent include water and N-methylpyrrolidone and / or dimethyl sulfoxide, and the water content is 5 wt% or more (preferably 5 wt% to 80 wt%, more preferably Is 5 to 30% by weight). In the present specification, the “solvent crack” refers to a crack generated when the mixed solvent is dropped on the transparent resin film and then left at room temperature for 5 minutes.

The refractive index (n _r ) at a wavelength of 550 nm of the transparent resin film of the present invention is preferably 1.5 to 1.8.

  The thickness of the transparent resin film of the present invention is preferably 1 μm to 60 μm, and more preferably 1 μm to 40 μm.

  The transparent resin film of the present invention may further contain any appropriate additive depending on the purpose. Examples of the additives include diluents, anti-aging agents, denaturing agents, surfactants, dyes, pigments, anti-discoloring agents, ultraviolet absorbers, softeners, stabilizers, plasticizers, antifoaming agents, reinforcing agents, and the like. Is mentioned. The kind, number, and amount of additives contained in the resin composition can be appropriately set depending on the purpose.

B. Transparent substrate
B-1. Overall Configuration of Transparent Substrate FIG. 1A is a schematic sectional view of a transparent substrate according to a preferred embodiment of the present invention. The transparent substrate 100 includes an inorganic glass 10 and transparent resin films 11 and 11 ′ disposed on one side or both sides of the inorganic glass 10 (preferably, both sides as in the illustrated example). As the transparent resin films 11 and 11 ′, the transparent resin film described in the above section A is used. In the present invention, by providing the transparent resin film, it is possible to obtain a transparent substrate that is excellent in flexibility and is less prone to cracks during cutting. Furthermore, the transparent resin film contains a layered silicate that has been subjected to organic treatment, thereby providing a transparent substrate capable of providing gas barrier properties to the transparent resin film and preventing gas from entering from the side of the transparent resin film. be able to. In addition, although not shown in figure, arbitrary appropriate adhesive bond layers may be arrange | positioned between the inorganic glass 10 and the transparent resin films 11 and 11 '.

  FIG. 1B is a schematic cross-sectional view of a transparent substrate according to another embodiment of the present invention. In this embodiment, the transparent substrate 101 includes layers 12 and 12 ′ including a coupling agent (hereinafter also referred to as a coupling agent layer) between the inorganic glass 10 and the transparent resin films 11 and 11 ′. Further prepare. Although not shown, any appropriate adhesive layer may be disposed between the transparent resin films 11 and 11 ′ and the coupling agent layers 12 and 12 ′.

  When the transparent substrate of the present invention includes the coupling agent layers 12 and 12 ', preferably, the coupling agent layers 12 and 12' are directly (that is, an adhesive) on the inorganic glass 10, as shown in FIG. Or without an adhesive). Thus, if the coupling agent layers 12 and 12 'are directly provided on the inorganic glass 10, the adhesiveness between the inorganic glass and the transparent resin film is excellent even in a high-temperature and high-humidity environment, and cracks develop during cutting. A difficult transparent substrate is obtained.

  FIG. 1C is a schematic cross-sectional view of a transparent substrate according to still another embodiment of the present invention. In this embodiment, the transparent substrate 102 is separated between the transparent resin films 11 and 11 ′ and the coupling agent layers 12 and 12 ′ (inorganic glass 10 when no coupling agent layer is provided). Resin layers 13 and 13 'are further provided. Preferably, the other resin layers 13 and 13 ′ include a resin that is compatible with the resin compound that forms the transparent resin films 11 and 11 ′.

  The transparent substrate of the present invention may be provided with any appropriate other layer as an outermost layer, if necessary. Examples of the other layers include a hard coat layer and a transparent conductive layer.

  The total thickness of the transparent substrate of the present invention is preferably 150 μm or less, more preferably 120 μm or less, and particularly preferably 50 μm to 120 μm. According to this invention, by having a transparent resin film as mentioned above, the thickness of inorganic glass can be made much thinner than the conventional glass substrate. That is, even if the transparent resin film is thin, it can contribute to the improvement of impact resistance and toughness, so that a transparent substrate that is lightweight and thin and has excellent impact resistance can be obtained.

  When the said transparent resin film is arrange | positioned at the both sides of the said inorganic glass, the thickness of each transparent resin film may be the same and may differ. Preferably, the thickness of each transparent resin film is the same. Furthermore, each transparent resin film may be comprised with the resin compound of the same composition, and may be comprised with the resin compound of a different composition. Preferably, each transparent resin film is comprised with the resin compound of the same composition. Therefore, most preferably, each transparent resin film is comprised so that it may become the same thickness with the resin compound of the same composition. With such a configuration, even when heat treatment is performed, thermal stress is evenly applied to both surfaces of the inorganic glass, and thus warpage and undulation are extremely unlikely to occur.

  The fracture diameter when the transparent substrate of the present invention is cracked and bent is preferably 50 mm or less, more preferably 40 mm or less, and particularly preferably 25 mm or less. The transparent substrate of the present invention exhibits excellent flexibility (for example, a fracture diameter in the above range) by including a specific transparent resin film.

  The total light transmittance of the transparent substrate of the present invention is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. Preferably, the transparent substrate has a reduction rate of light transmittance of 5% or less after heat treatment at 180 ° C. for 2 hours. This is because with such a reduction rate, a practically acceptable light transmittance can be ensured even if the heat treatment necessary in the FPD manufacturing process is performed.

  The haze value of the transparent substrate of the present invention is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 2% or less.

  The surface roughness Ra of the transparent substrate of the present invention (substantially, the surface roughness Ra of the transparent resin film or the other layer) is preferably 50 nm or less, more preferably 30 nm or less, particularly preferably 10 nm. It is as follows. The waviness of the transparent substrate is preferably 0.5 μm or less, and more preferably 0.1 μm or less. A transparent substrate having such characteristics is excellent in quality. Such characteristics can be realized, for example, by a manufacturing method described later.

  The transparent substrate of the present invention has a linear expansion coefficient of preferably 15 ppm / ° C. or less, more preferably 10 ppm / ° C. or less, and particularly preferably 1 ppm / ° C. to 10 ppm / ° C. By providing the inorganic glass, the transparent substrate exhibits excellent step stability (for example, linear expansion coefficient in the above range). More specifically, in addition to the fact that the inorganic glass itself is rigid, the dimensional fluctuation of the transparent resin film can be suppressed by restraining the transparent resin film by the inorganic glass. As a result, the transparent substrate as a whole exhibits excellent dimensional stability.

B-2. Inorganic glass As long as the inorganic glass used for the transparent substrate of this invention is a plate-shaped thing, arbitrary appropriate things may be employ | adopted. Examples of the inorganic glass include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass according to the classification according to the composition. Moreover, according to the classification | category by an alkali component, an alkali free glass and a low alkali glass are mentioned. The content of alkali metal components (for example, Na ₂ O, K ₂ O, Li ₂ O) in the inorganic glass is preferably 15% by weight or less, and more preferably 10% by weight or less.

  The thickness of the inorganic glass is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 20 μm to 80 μm, and particularly preferably 30 μm to 70 μm. In this invention, the thickness of inorganic glass can be made thin by having a transparent resin film in the one side or both sides of inorganic glass.

The light transmittance of the inorganic glass at a wavelength of 550 nm is preferably 85% or more. The refractive index _ng of the inorganic glass at a wavelength of 550 nm is preferably 1.4 to 1.65.

The density of the inorganic glass is preferably ^{2.3g / cm 3 ~3.0g / cm 3} , more preferably from ^{2.3g / cm 3 ~2.7g / cm 3} . If it is the inorganic glass of the said range, a lightweight transparent substrate will be obtained.

  Arbitrary appropriate methods may be employ | adopted for the shaping | molding method of the said inorganic glass. Typically, the inorganic glass is a mixture of a main raw material such as silica or alumina, an antifoaming agent such as sodium nitrate or antimony oxide, and a reducing agent such as carbon at a temperature of 1400 ° C to 1600 ° C. Then, after forming into a thin plate shape, it is produced by cooling. Examples of the method for forming the inorganic glass sheet include a slot down draw method, a fusion method, and a float method. The inorganic glass formed into a plate shape by these methods may be chemically polished with a solvent such as hydrofluoric acid, if necessary, in order to reduce the thickness or improve the smoothness.

  As the inorganic glass, a commercially available one may be used as it is, or a commercially available inorganic glass may be polished to have a desired thickness. Examples of commercially available inorganic glasses include “7059”, “1737” or “EAGLE 2000” manufactured by Corning, “AN100” manufactured by Asahi Glass, “NA-35” manufactured by NH Techno Glass, and “OA-” manufactured by Nippon Electric Glass. 10 ”,“ D263 ”or“ AF45 ”manufactured by Schott Corporation.

B-3. Adhesive Layer Any appropriate resin can be adopted as the material constituting the adhesive layer. Examples of the material constituting the adhesive layer include a thermosetting resin, a thermoplastic resin, an active energy ray curable resin, and the like. Specific examples of such resins include epoxy resins containing epoxies and / or oxetanes; acrylic resins; silicone resins. An epoxy resin excellent in heat resistance is preferable. In addition, you may use these resin individually or in combination of 2 or more types. In one embodiment, an adhesive layer is formed by using an epoxy resin and a thermoplastic resin together. If such an adhesive layer is formed, stronger adhesion can be realized.

  The thermal decomposition temperature of the adhesive layer is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, particularly preferably 200 ° C. or higher, and most preferably 200 ° C. to 350 ° C. If it is such a range, the transparent substrate excellent in heat resistance can be obtained.

  The thickness of the adhesive layer is preferably 10 μm or less, more preferably 0.01 μm to 10 μm, and particularly preferably 0.1 μm to 7 μm. If the thickness of the said adhesive bond layer is such a range, the outstanding adhesiveness of the said inorganic glass and the said transparent resin film can be implement | achieved, without impairing the flexibility of a transparent substrate.

B-4. Coupling agent layer Preferably, the transparent substrate of the present invention further comprises a coupling agent layer between the transparent resin film and the inorganic glass. More preferably, the coupling agent layer is directly disposed on the inorganic glass.

  Examples of the coupling agent include at least one coupling agent selected from the group consisting of an epoxy group-containing coupling agent, an amino group-containing coupling agent, and an isocyanate group-containing coupling agent. The substitution position of the amino group, epoxy group and isocyanate group of these coupling agents may or may not be the end of the molecule. With such a coupling agent, the transparent resin film can be firmly adhered to the inorganic glass via the coupling agent layer.

  A commercially available product may be used as the coupling agent. As a commercially available epoxy group-containing coupling agent, for example, trade name “KBM-303” (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403” (3-glycidoxypropyltrimethoxysilane), trade name “KBE-402” (3-glycidoxypropylmethyldiethoxysilane), trade name “KBE-403” (3-glycidoxypropyltriethoxysilane) Is mentioned. Examples of commercially available amino group-containing coupling agents include those manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-602” (N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane), and trade name “KBM-”. 603 "(N-2- (aminoethyl) -3-aminopropyltrimethoxysilane), trade name" KBE-603 "(N-2- (aminoethyl) -3-aminopropyltriethoxysilane), trade name" KBM-903 "(3-aminopropyltrimethoxysilane), trade name" KBE-903 "(3-aminopropyltriethoxysilane), trade name" KBM-573 "(N-phenyl-3-aminopropyltrimethoxysilane) ) And trade name "KBE-9103" (3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine) Is mentioned. As a commercially available isocyanate group containing coupling agent, the Shin-Etsu Chemical Co., Ltd. make and brand name "KBE-9007" (3-isocyanate propyl triethoxysilane) is mentioned, for example.

  The thickness of the coupling agent layer is preferably 0.001 μm to 10 μm, and more preferably 0.001 μm to 2 μm.

B-5. Another resin layer In one embodiment, the transparent substrate of the present invention further includes another resin layer between the inorganic glass and the transparent resin film. If another resin layer is provided, when the transparent resin film is formed by solution coating, the other resin layer and the transparent resin film are compatible with each other, so that a transparent substrate with high adhesion can be easily obtained. Can do.

  The another resin layer preferably contains a thermoplastic resin and an epoxy-based end coupling agent. The said thermoplastic resin is a thermoplastic resin which can react with the coupling agent contained in the said coupling agent layer, and / or the epoxy-type terminal coupling agent contained in the said another resin layer. Examples of such a thermoplastic resin include a thermoplastic resin having a hydroxyl group at the terminal and a thermoplastic resin having a carboxylic acid at the terminal and / or side chain.

  Specific examples of the thermoplastic resin having a hydroxyl group at the terminal include thermoplastic resins obtained by modifying the terminal hydroxyl group of polyethersulfone, polyimide, polyimideamide, polyetherimide, polysulfone, polyarylate, polycarbonate and the like. These thermoplastic resins can be used alone or in admixture of two or more. If such a thermoplastic resin is used, a resin layer having excellent adhesion to the inorganic glass or the coupling agent layer and excellent toughness can be obtained even in a high temperature and high humidity environment. If a resin layer having excellent toughness is used in this way, it is possible to obtain a transparent substrate in which cracks at the time of cutting hardly progress. In addition, arbitrary appropriate methods may be used for the said terminal hydroxyl group modification | denaturation.

  The hydroxyl group present at the terminal is preferably a phenolic hydroxyl group. When the thermoplastic resin having a hydroxyl group at the terminal has a phenolic hydroxyl group at the terminal, a strong interaction with an epoxy-based terminal coupling agent contained in another resin layer can be obtained.

  The content of the hydroxyl group is preferably 0.3 or more, more preferably 0.5 to 2.0, per 100 degree of polymerization of the thermoplastic resin having a hydroxyl group at the terminal. When the content of the hydroxyl group is within such a range, an excellent interaction with the epoxy-based end coupling agent can be obtained.

  A commercially available product may be used as the thermoplastic resin having a hydroxyl group at the terminal. Examples of the thermoplastic resin having a phenolic hydroxyl group at a commercially available terminal include “Sumika Excel 5003P” manufactured by Sumitomo Chemical Co., Ltd.

  The glass transition temperature of the thermoplastic resin contained in the other resin layer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, particularly preferably 220 ° C. or higher, and most preferably 220 ° C. to 350 ° C. ° C. If it is such a range, the transparent substrate excellent in heat resistance can be obtained.

  As said epoxy-type terminal coupling agent, the epoxy group containing coupling agent which has the epoxy group as described in the said B-4 term | term is mentioned, for example.

  The content of the epoxy-based end coupling agent is preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin contained in another resin layer. Parts, more preferably 20 parts by weight to 35 parts by weight. By making content of an epoxy type terminal coupling agent into said range, the adhesiveness of inorganic glass and a resin layer can fully be improved. Furthermore, even if the total thickness of the transparent substrate is increased, a transparent substrate having a desired haze value can be obtained.

  The another resin layer preferably further includes a cyclic ether compound and / or a compound in which a cyclic portion of the cyclic ether compound is opened. If the cyclic ether compound and / or the compound in which the cyclic portion of the cyclic ether compound is opened, the other resin layer and the coupling agent layer or the inorganic glass can be stably adhered, so that the yield is high. A transparent substrate can be obtained.

  Any appropriate compound can be used as the cyclic ether compound. Examples of the cyclic ether compound include 6-membered cyclic ether compounds such as oxetanes, 5-membered cyclic ether compounds such as tetrahydrofurans, and tetrahydropyrans. Examples include membered cyclic ether compounds and epoxies. As the compound in which the cyclic portion of the cyclic ether compound is opened, those obtained by opening any appropriate cyclic ether compound can be used, and examples thereof include compounds obtained by opening the cyclic ether compound. Any appropriate method is used as the ring-opening method of the cyclic ether compound.

  The content of the cyclic ether compound and / or the compound in which the cyclic portion of the cyclic ether compound is opened is preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin having a hydroxyl group at the terminal. More preferably, it is 5-30 weight part, More preferably, it is 5-20 weight part. By setting the content of the cyclic ether compound and / or the compound in which the cyclic portion of the cyclic ether compound is opened in the above range, coloring of the resin layer derived from the cyclic ether compound under heating can be suppressed.

The transmittance of the other resin layer at a wavelength of 550 nm is preferably 80% or more. The refractive index (n _r ) at a wavelength of 550 nm of the other resin layer is preferably 1.5 to 1.8.

  The elastic modulus at 25 ° C. of the other resin layer is preferably 1 GPa or more, and more preferably 1.5 GPa or more. By setting it as the above range, even when the inorganic glass is thinned, the local stress in the tearing direction to the defect generated when another resin layer is deformed is relieved, so that the inorganic glass is hardly cracked and broken.

The fracture toughness value at 25 ° C. of the other resin layer is preferably 1 MPa · m ^{1/2 to} 10 MPa · m ^1/2 , and more preferably 1.5 MPa · m ^{1/2 to} 6 MPa · m ^1/2. It is.

  The thickness of the other resin layer is preferably 20 μm or less. By setting the thickness of the other resin layer within the above range, sufficient adhesion between the inorganic glass or the coupling agent layer and the resin layer can be obtained even in a high temperature and high humidity environment. The thickness of another resin layer is more preferably 0.001 μm to 20 μm, still more preferably 0.001 μm to 15 μm, and particularly preferably 0.01 μm to 10 μm. If it is said preferable range, the transparent substrate which satisfies sufficient transparency can be obtained.

  When the other resin layers are disposed on both sides of the inorganic glass, the thickness of each of the other resin layers may be the same or different. Preferably, the thickness of each separate resin layer is the same. Furthermore, each separate resin layer may be comprised with the resin compound of the same composition, and may be comprised with a different composition resin compound. Preferably, each of the different resin layers is composed of a resin compound having the same composition. Therefore, most preferably, each of the different resin layers is configured to have the same thickness with a resin compound having the same composition. With such a configuration, even when heat treatment is performed, thermal stress is evenly applied to both surfaces of the inorganic glass, and thus warpage and undulation are extremely unlikely to occur.

  The another resin layer may further contain any appropriate additive depending on the purpose. As the additive, an additive similar to the additive described in the section A-3 can be used.

B-6. Other Layers The transparent substrate may include any appropriate other layer as necessary. Examples of the other layers include a transparent conductive layer and a hard coat layer.

  The transparent conductive layer can function as an electrode or an electromagnetic wave shield.

  Examples of materials that can be used for the transparent conductive layer include metals such as copper and silver; metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO); and conductive materials such as polythiophene and polyaniline. Examples of the polymer include a composition containing carbon nanotubes.

  The hard coat layer has a function of imparting chemical resistance, scratch resistance and surface smoothness to the transparent substrate.

  Any appropriate material can be adopted as the material constituting the hard coat layer. Examples of the material constituting the hard coat layer include an epoxy resin, an acrylic resin, a silicone resin, and a mixture thereof. Among these, an epoxy resin excellent in heat resistance is preferable. The hard coat layer can be obtained by curing these resins with heat or active energy rays.

B-7. Production method of transparent substrate The transparent substrate of the present invention is dispersed on the inorganic glass, as described in the section A-3, a highly polar solvent, a resin compound dissolved in the highly polar solvent, and the highly polar solvent. It can obtain by applying the coating liquid containing the organically-processed layered silicate. Moreover, the transparent resin film formed on another base material may be stuck on inorganic glass through an adhesive bond layer, and a transparent substrate may be formed.

  When the transparent substrate of the present invention includes a coupling agent layer, the surface of the inorganic glass may be subjected to a coupling treatment before forming the transparent resin film. The coupling agent is as described in the section B-4.

  Any appropriate method can be adopted as the method of the coupling treatment. Specifically, for example, there is a method in which a solution of the coupling agent is applied to the surface of the inorganic glass and then heat-treated.

  As a solvent used when preparing the solution of the coupling agent, any appropriate solvent can be used as long as it does not react with the coupling agent. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane and hexadecane; aromatic solvents such as benzene, toluene and xylene; halogen hydrocarbon solvents such as methylene chloride and 1,1,2-trichloroethane; tetrahydrofuran And ether solvents such as 1,4-dioxane; alcohol solvents such as methanol and propanol; ketone solvents such as acetone and 2-butanone; and water.

  Any appropriate heat treatment method can be adopted as the heat treatment method in the coupling treatment. Typically, the heat treatment temperature is 50 ° C. to 150 ° C., and the heat treatment time is 1 minute to 10 minutes. By the heat treatment, the coupling agent and the inorganic glass surface can be bonded by chemical bonding.

  When a transparent substrate is provided with another resin layer, it is preferable to form a transparent resin film after forming another resin layer on the surface of the inorganic glass or the inorganic glass subjected to the coupling treatment. As another method for forming the resin layer, for example, a coating step for applying another casting solution for a resin layer on the surface of the inorganic glass to form a coating layer, a drying step for drying the coating layer, and a step after drying And a heat treatment step of heat-treating the coating layer.

  Examples of the coating solvent used in the coating step of the other resin layer casting solution include ketone solvents, halogen solvents, aromatic solvents, highly polar solvents, and mixtures thereof. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the halogen solvent include methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, trichloroethane, and the like. Examples of the aromatic solvent include toluene, xylene, benzene, phenol and the like. Examples of the highly polar solvent include dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, ethyl acetoacetate, dimethylacetamide and the like.

  As a coating method for forming the other resin layer, a method similar to the coating method for forming the transparent resin film may be employed.

  Any appropriate drying method (for example, natural drying, air drying, heat drying) may be employed as a drying method for forming the other resin layer. For example, in the case of heat drying, the drying temperature is typically 80 ° C. to 150 ° C., and the drying time is typically 1 minute to 30 minutes. While being dried, the epoxy-based end coupling agent and the thermoplastic resin having a hydroxyl group at the terminal can be reacted.

  Any appropriate heat treatment method can be adopted as the heat treatment method in forming the other resin layer. Typically, the heat treatment temperature is 100 ° C. to 250 ° C., and the heat treatment time is 1 minute to 20 minutes. By the heat treatment, the epoxy group terminal coupling agent and the inorganic glass surface can be bonded by chemical bonding.

  When the transparent substrate includes another resin layer, preferably, a drying step of further drying the formed transparent resin film and another resin layer, and a heat treatment step of heat-treating the dried transparent resin film and another resin layer are performed. Including. By including these steps, the chemical bond or interaction between the inorganic glass, the transparent resin film, and another resin layer can be further strengthened. Any appropriate method described above can be adopted as the drying method. In the case of the heat drying method, the drying temperature is typically 80 ° C. to 150 ° C., and the drying time is typically 1 minute to 30 minutes. It is. Any appropriate heat treatment method can be adopted as the heat treatment method. Typically, the heat treatment temperature is 100 ° C. to 250 ° C., and the heat treatment time is 1 minute to 20 minutes.

  When a transparent substrate is manufactured by sticking a transparent resin film formed on another base material onto an inorganic glass, the transparent substrate is produced by applying the transparent resin film on one side or both sides of the inorganic glass. A bonding step of bonding through a body layer, and an adhesive curing step of curing the adhesive precursor layer by active energy ray irradiation or heat treatment to form an adhesive layer. The transparent resin film may be annealed before or after being bonded to the inorganic glass. By performing the annealing treatment, impurities such as residual solvent and unreacted monomer components can be efficiently removed. The temperature of the annealing treatment is preferably 100 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C. Moreover, the treatment time of the annealing treatment is preferably 5 minutes to 20 minutes.

  As a material constituting the adhesive precursor layer, the resin described in the section B-3 can be used.

  In the said sticking process, after coating the said adhesive agent precursor on the said transparent resin film, you may stick an adhesive agent precursor layer and inorganic glass, and the said adhesive agent precursor is said inorganic glass. After coating on top, you may stick an adhesive precursor layer and inorganic glass.

As a method of the above-mentioned active energy ray irradiation, for example, irradiation integrated light quantity and a method for irradiating ultraviolet rays of ^{100mJ / cm 2 ~2000mJ / cm 2} 1 to 10 minutes.

  The conditions for the heat treatment are typically a heating temperature of 100 ° C. to 200 ° C. and a heating time of 5 minutes to 30 minutes.

  The manufacturing method of the transparent substrate of this invention includes the process of forming arbitrary appropriate other layers further on a transparent resin film according to a use. Examples of other layers include the transparent conductive layer and the hard coat layer exemplified in the above section B-6. Any appropriate method can be used as a method of forming other layers.

C. Applications The transparent substrate of the present invention can be used for any appropriate display element, solar cell or lighting element. Examples of the display element include a liquid crystal display, a plasma display, an organic EL display, and electronic paper. As an illumination element, an organic EL element etc. are mentioned, for example.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. The evaluation methods in the examples are as follows. The thickness was measured using an Anritsu digital micrometer “KC-351C type”.

(1) Total light transmittance The total light transmittance of the transparent resin film was measured according to JIS R3106-1998 using U-4100 made by Hitachi, Ltd.
(2) Haze value The haze value of the transparent resin film was measured according to JIS K7136 using a haze meter “HM-150” manufactured by Murakami Color Research Laboratory.
(3) Colorability The obtained transparent resin film was placed at 200 ° C. for 1 hour, and then the b value in the hunter color system of the transparent substrate was measured to evaluate the presence or absence of coloring. The b value was measured using a high-speed integrating sphere type spectral transmittance measuring device “DOT-3C” manufactured by Murakami Color Research Laboratory.
(4) Gas barrier properties (moisture permeability)
Evaluation was made by the MOCON measurement method based on JIS K7129B. Specifically, it was measured using a water vapor permeability measuring device “PERMATRAN W3 / 33MG type (with HRH-1D type high precision flow rate control device)” manufactured by MOCON. The humidity condition was 40 ° C. and 90% RH, the gas flow rate was 10.0 ± 0.5 cc / min, and the measurement time was 20 hours or more.
(5) Storage stability An organic EL device using, as a cover layer (sealing material), a glass with a transparent resin film obtained by attaching the transparent resin film obtained in Example 1 and Comparative Example 1 below to glass. Produced. Specifically, a transparent electrode as an anode was formed on a glass substrate, a light emitting layer was formed on the transparent electrode, and a metal electrode as a cathode was formed on the light emitting layer to obtain a laminate. . The glass with a transparent resin film was used as a sealing material, and the laminate was sealed such that the transparent resin film was on the laminate side to obtain an organic EL element. In addition, the organic EL element was produced without using a hygroscopic agent.
This organic EL element was left in an environment of 60 ° C./90% RH for 168 hours, and the length of the dark frame was measured. The short length of the dark frame indicates excellent storage stability, that is, excellent gas barrier properties.

[Production Example 1] Synthesis of resin compound In a reaction vessel equipped with a stirrer, 7.65 g (0.028 mol) of 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-(1- 12.35 g (0.043 mol) of phenylethylidene) bisphenol, 0.444 g of benzyltriethylammonium chloride and 0.022 g of p-tertiary butylphenol were dissolved in 185 g of 1M sodium hydroxide solution. To this solution, a solution of 14.4 g (0.071 mol) of terephthalic acid chloride dissolved in 246 g of chloroform was added all at once with stirring, followed by stirring at room temperature for 120 minutes. Thereafter, the chloroform solution containing the resin compound was separated by stationary separation, and the chloroform solution was washed in turn with acetic acid water and ion-exchanged water, and then the chloroform solution was poured into methanol to precipitate the resin compound. The precipitated resin compound was filtered and dried under reduced pressure to obtain 27 g of a white resin compound A.

[Production Example 2] Preparation of organically treated layered silicate dispersion 10 g of layered silicate (trade name “Kunipia F”, manufactured by Kunimine Kogyo Co., Ltd.) was dispersed in water at a concentration of 2%, and an organic treatment agent (1 -Decyle-3-methylimidazolium chloride) (3.9 g) was added, and the mixture was stirred at 80 ° C. for 2 hours. The dispersion was centrifuged and the precipitate was washed with water. Subsequently, 500 g of acetone was added and subjected to ultrasonic treatment, and then the precipitate (organized layered silicate) was collected by centrifuging again. 10.5 g of organically treated layered silicate and 200 g of dimethylacetamide were mixed to obtain an organically treated layered silicate dispersion having a concentration of 5% by weight of organically treated layered silicate.

[Production Example 3] Preparation of organically treated layered silicate dispersion liquid An organically treated layered silicate dispersion liquid was obtained in the same manner as in Production Example 2 except that dimethylformamide was used instead of dimethylacetamide. .

[Production Example 4] Preparation of organically treated layered silicate dispersion liquid An organically treated layered silicate dispersion liquid was obtained in the same manner as in Production Example 2 except that toluene was used instead of dimethylacetamide.

[Example 1]
A dimethylacetamide solution of the resin compound obtained in Production Example 1 (polymer concentration: 20% by weight, relative dielectric constant: 38) was added little by little to the organically treated layered silicate dispersion obtained in Production Example 2. A transparent coating solution was prepared. The content ratio of the organically treated layered silicate was 5 parts by weight with respect to 100 parts by weight of the resin compound.
The obtained coating liquid was applied to a glass substrate, dried at 100 ° C. for 10 minutes, then at 180 ° C. for 20 minutes, and then peeled from the glass substrate to obtain a transparent resin film (thickness 27 μm). .
The obtained transparent resin film was subjected to the evaluations (1) to (4). The results are shown in Table 1.
Moreover, the obtained transparent resin film was used for the said evaluation (5). The results are shown in FIG. In addition, in FIG. 2, the storage stability at the time of using the sealing material formed only from glass is also shown for reference. Furthermore, the TEM photograph of the obtained transparent resin film cross section is shown in FIG.

[Example 2]
A transparent resin film was obtained in the same manner as in Example 1 except that the content of the organically treated layered silicate was 10 parts by weight with respect to 100 parts by weight of the resin compound. The obtained transparent resin film was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Example 3]
A transparent resin film was obtained in the same manner as in Example 1 except that the content of the organically treated layered silicate was 13 parts by weight with respect to 100 parts by weight of the resin compound. The obtained transparent resin film was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Example 4]
The organically treated layered silicate dispersion obtained in Production Example 2 was added to a toluene / dimethyl sulfoxide solution of the polymer obtained in Production Example 1 (polymer concentration: 20 wt%, solvent ratio (weight ratio; toluene: dimethyl sulfoxide). ) = 7: 3, relative dielectric constant: 16) was added little by little to prepare a transparent coating solution. The content ratio of the organically treated layered silicate was 10 parts by weight with respect to 100 parts by weight of the polymer. A transparent resin film was obtained in the same manner as in Example 1 except that the coating liquid thus obtained was used. The obtained transparent resin film was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Example 5]
The organically treated layered silicate dispersion obtained in Production Example 2 was added to the toluene / dimethylacetamide solution of the polymer obtained in Production Example 1 (polymer concentration: 20% by weight, solvent ratio (weight ratio; toluene: dimethylacetamide). ) = 7: 3, relative dielectric constant: 13) was added little by little to prepare a transparent coating solution. A transparent resin film was obtained in the same manner as in Example 1 except that the coating liquid thus obtained was used. The obtained transparent substrate was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Example 6]
The organically treated layered silicate dispersion obtained in Production Example 3 was added to the toluene / dimethyl sulfoxide solution of the polymer obtained in Production Example 1 (polymer concentration: 20 wt%, solvent ratio (weight ratio; toluene: dimethyl sulfoxide). ) = 7: 3, relative dielectric constant: 16) was added little by little to prepare a transparent coating solution. A transparent resin film was obtained in the same manner as in Example 1 except that the coating liquid thus obtained was used. The obtained transparent substrate was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Comparative Example 1]
A dimethylacetamide solution of the polymer obtained in Production Example 1 (polymer concentration: 20% by weight) was used as a coating solution. A transparent resin film was obtained in the same manner as in Example 1 except that the coating solution was used. The obtained transparent resin film was subjected to the above evaluations (1) to (4). The results are shown in Table 1. Moreover, the obtained transparent resin film was used for the said evaluation (6).

[Comparative Example 2]
To the organically treated layered silicate dispersion obtained in Production Example 4, the toluene solution of the polymer obtained in Production Example 1 (polymer concentration: 20% by weight) was added little by little to prepare a transparent coating solution. did. The content ratio of the organically treated layered silicate was 10 parts by weight with respect to 100 parts by weight of the polymer. A transparent resin film was obtained in the same manner as in Example 1 except that the coating liquid thus obtained was used. The obtained transparent resin film was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Comparative Example 3]
To the organically treated layered silicate dispersion obtained in Production Example 2, the toluene solution of the polymer obtained in Production Example 1 (polymer concentration: 20% by weight, relative dielectric constant: 2.3) was added little by little. A transparent coating solution was prepared. The content ratio of the organically treated layered silicate was 10 parts by weight with respect to 100 parts by weight of the polymer. A transparent resin film was obtained in the same manner as in Example 1 except that the coating liquid thus obtained was used. The obtained transparent substrate was subjected to the above evaluations (1) to (4). The results are shown in Table 1.

[Comparative Example 4]
Instead of the organically treated layered silicate dispersion obtained in Production Example 2, the organically treated layered silicate dispersion obtained in Production Example 3 was used in the same manner as in Comparative Example 3, A transparent resin film was obtained. The obtained transparent resin film was subjected to the evaluations (1) to (4). The results are shown in Table 1.

  The transparent resin film of this invention can be used for a display element, a solar cell, or a lighting element. Examples of the display element include a liquid crystal display, a plasma display, an organic EL display, and electronic paper. As an illumination element, an organic EL element etc. are mentioned, for example.

DESCRIPTION OF SYMBOLS 10 Inorganic glass 11, 11 'Transparent resin film 12, 12' Coupling agent layer 13, 13 'Another resin layer 100, 101, 102 Transparent substrate

Claims (19)

Formed by coating a coating solution containing a highly polar solvent, a resin compound dissolved in the highly polar solvent, and an organically treated layered silicate,
The relative dielectric constant of the highly polar solvent is 10 or more,
The content ratio of the organically treated layered silicate is 1 to 30 parts by weight with respect to 100 parts by weight of the resin compound.
Transparent resin film.   The transparent resin film of Claim 1 whose light transmittance in wavelength 550nm is 70% or more.   The transparent resin film of Claim 1 or 2 whose haze value is 10% or less.   The transparent resin film in any one of Claim 1 to 3 whose elasticity modulus in 25 degreeC is 1.5GPa-10GPa. Fracture toughness value at 25 ° C. ^is a ^{1.5MPa · m 1/2 ~10MPa · m 1/2} , a transparent resin film according to any one of claims 1 to 4.   The solvent crack does not occur when contacted with a mixed solvent containing water and N-methylpyrrolidone and / or dimethyl sulfoxide and having a water content of 5% by weight or more. The transparent resin film as described.   The organically treated layered silicate is subjected to an organic treatment using a quaternary imidazolium salt and / or a quaternary phosphonium salt as an organic treatment agent. The transparent resin film as described.   The transparent resin film in any one of Claim 1 to 7 whose glass transition temperature of the said resin compound is 180 to 450 degreeC. The weight average molecular weight of the resin compound is 2 × 10 ⁴ ~100 × 10 ⁴ in terms of polystyrene, a transparent resin film according to any of claims 1 to 8. The transparent resin film according to any one of claims 1 to 9, wherein the resin compound has a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2):
In Formula (1), R ¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, R ² is a linear or branched alkyl group having 2 to 5 carbon atoms, and A ¹ And A ² are each independently at least one selected from the linking groups represented by the above general formulas (3) to (7), X ¹ is an arylene group, and X ¹ is a para- or meta- Linked to the linking group A ² and the linking group A ¹ or A ³ at the position;
In Formula (2), R ³ is a methyl group or an aryl group, and A ³ and A ⁴ are each independently at least one selected from the linking groups represented by Formulas (3) to (7). X ² is an arylene group, and X ² is linked to the linking group A ⁴ and the linking group A ¹ or A ³ at the para or meta position. In the resin compound, the total number of X ¹ and X ² having a linking group at the para-position, relative to the total number of X ¹ and X ² having a linking group in the meta position, more than three times, according to claim 10 The transparent resin film as described in 2. In the resin compound, R ¹ is a methyl group, R ² is an isobutyl group, R ³ is a methyl group or an aryl group, and each of A ¹ , A ² , A ³ and A ⁴ is independently A linking group represented by formula (3) or (4), wherein X ¹ is an aryl group linked to linking group A ² and linking group A ¹ or A ^{3 in the} para position, and X ² is in the para position an aryl group linked to the linking group a ⁴ and the linking group a ¹ or a ^3, a transparent resin film according to claim 10 or 11. The transparent resin film according to any one of claims 10 to 12, wherein the resin compound further has a repeating unit represented by the general formula (8):
In formula (8), R ⁴ and R ⁵ are each independently a methyl group or hydrogen, and B is a substituted or unsubstituted cycloalkane having 4 to 9 carbon atoms, or substituted or unsubstituted fluorene.   A transparent substrate comprising inorganic glass having a thickness of 100 μm or less and the transparent resin film according to claim 1 disposed on one side or both sides of the inorganic glass.   The transparent substrate according to claim 14, wherein the total thickness is 150 μm or less.   The transparent substrate according to claim 14 or 15, wherein a fracture diameter when the transparent substrate is cracked and bent is 50 mm or less.   A display device produced using the transparent substrate according to claim 14.   A solar cell produced using the transparent substrate according to claim 14. An illumination element manufactured using the transparent substrate according to claim 14.