JP2015168153A - resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film including both a thermoplastic resin layer and a hardening resin layer, and excellent in heat resistance and yellow discoloration resistance.SOLUTION: A resin film includes a thermoplastic resin layer made from thermoplastic resin, and a hardening resin layer arranged on the thermoplastic resin layer. A glass transformation temperature of the thermoplastic resin is 250°C or more, a total light transmittance of the thermoplastic resin layer is 85% or more, and a hue change when heating the thermoplastic resin layer in air from 25°C to 250°C is 2 or less at a hue b value. The hardening resin layer is made by hardening a hardening resin composition containing curable monomer and/or curable oligomer, a content ratio of a solvent in the hardening resin composition is 1 wt.% or less in the total weight of the hardening resin composition, and a storage elastic modulus of the hardening resin layer at 250°C is 20% or more to a storage elastic modulus at 30°C.

Description

  The present invention relates to a resin film.

  Conventionally, as a substrate of an image display device such as a flat panel display (FPD: liquid crystal display device, organic EL display device), a solar cell, an organic EL lighting device, etc., a resin film, a composite of a resin film and an inorganic material Etc. are used (for example, Patent Document 1).

  The resin film used as the substrate is required to have transparency and heat resistance, and a highly transparent and high heat resistant thermoplastic resin (for example, polyethersulfone) is used as the resin constituting the resin film. . However, such thermoplastic resins tend to turn yellow at high temperatures in the atmosphere. Therefore, in the process of manufacturing a resin film, it is necessary to take measures such as performing a heat treatment for a long time without raising the treatment temperature, in an environment where the thermoplastic resin is not oxidized, such as under nitrogen or vacuum, at the time of high temperature treatment. Become. In order to solve such a problem, development of a thermoplastic resin excellent in yellowing resistance has been studied.

  On the other hand, a resin film composed of a thermoplastic resin may be provided with a hard coat layer in order to improve scratch resistance, heat resistance, solvent resistance, and the like. A curable resin composition may be used for forming the hard coat layer, but there is a problem that solvent cracks occur in the thermoplastic resin film due to the solvent contained in the curable resin composition.

  Furthermore, in addition to avoiding solvent cracks, the hard coat layer is required to have yellowing resistance, adhesion to a thermoplastic resin layer, low shrinkage during curing, and the like. It is difficult to form a hard coat layer that satisfies these requirements in combination with a thermoplastic resin layer excellent in yellowing resistance (for example, having a high glass transition temperature).

JP 2011-152893 A

  The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is a resin film including a thermoplastic resin layer and a curable resin layer, which is excellent in heat resistance and yellowing resistance. It is to provide a resin film.

The resin film of the present invention comprises a thermoplastic resin layer formed from a thermoplastic resin and a curable resin layer disposed on the thermoplastic resin layer, and the glass transition temperature of the thermoplastic resin is 250 ° C. The total light transmittance of the thermoplastic resin layer is 85% or more, and the hue change when the thermoplastic resin layer is heated in air from 25 ° C. to 250 ° C. is the hue b value. 2 or less, and the curable resin layer is formed by curing a curable resin composition containing a curable monomer and / or a curable oligomer, and the solvent content in the curable resin composition is It is 1 weight% or less with respect to the whole quantity of this curable resin composition, and the storage elastic modulus in 250 degreeC of this curable resin layer is 20% or more with respect to the storage elastic modulus in 30 degreeC.
In one embodiment, the hue change when the resin film of the present invention is heated from 25 ° C. to 250 ° C. is 2 or less in hue b value.
In one embodiment, the surface of the thermoplastic resin layer on the side of the curable resin layer is subjected to surface modification treatment, and the surface modification treatment is corona treatment, UV treatment, or plasma treatment.
In one embodiment, the curable resin layer is a layer obtained by curing the curable resin composition with active energy rays.
In one embodiment, the curable resin layer is a layer obtained by curing the curable resin composition at a temperature of 150 ° C. or higher.
In one embodiment, the curable resin layer is a layer formed by bringing a sheet having a surface roughness Ra of 100 nm or less into contact with the curable resin composition when the curable resin composition is cured. .
In one embodiment, the curable tree composition contains a cage silsesquioxane-based oligomer.
In one embodiment, the cage silsesquioxane-based oligomer has an oxetanyl group.
In one embodiment, the said curable resin composition contains an alicyclic epoxy monomer.
In one embodiment, the curable resin composition further includes a photocation generator and a thermal cation generator, and the content ratio of the photocation generator is the curable resin composition in the curable resin composition. 1 part by weight to 3 parts by weight with respect to 100 parts by weight of the total amount of the monomer and the curable oligomer, and the content ratio of the thermal cation generator is the above curable monomer and curable oligomer in the curable resin composition The total amount is 1 part by weight to 5 parts by weight with respect to 100 parts by weight.
In one embodiment, in the said curable resin composition, content of the said thermal cation generator is larger than the content rate of the said photo cation generator.
According to another aspect of the present invention, a transparent substrate is provided. The transparent substrate includes inorganic glass and the resin film.

  According to the present invention, it is possible to provide a resin film that includes a thermoplastic resin layer and a curable resin layer and is excellent in heat resistance and yellowing resistance.

It is a schematic sectional drawing of the resin film by one Embodiment of this invention.

A. Overall Configuration of Resin Film FIG. 1 is a schematic sectional view of a resin film according to one embodiment of the present invention. The resin film 100 includes a thermoplastic resin layer 10 containing a thermoplastic resin, and a curable resin layer 20 disposed on the thermoplastic resin layer 10.

  Preferably, as in the illustrated example, the curable resin layer is directly disposed on the thermoplastic resin layer. In the present invention, as will be described later, when the curable resin layer is formed, it is difficult for solvent cracks to occur in the thermoplastic resin layer, and the adhesiveness of the curable resin layer to the thermoplastic resin layer is high. Even if the layer is arranged directly on the thermoplastic resin layer, a resin film can be obtained without any particular problem, and the effect of the present invention becomes more remarkable by adopting such an arrangement.

  The thickness of the resin film of the present invention is preferably 5 μm to 500 μm, more preferably 10 μm to 300 μm, and still more preferably 20 μm to 100 μm.

  The thickness of the thermoplastic resin layer is preferably 1 μm to 400 μm, more preferably 5 μm to 200 μm, and still more preferably 10 μm to 100 μm.

  The thickness of the curable resin layer is preferably 1 μm to 200 μm, more preferably 3 μm to 100 μm, and still more preferably 5 μm to 50 μm.

  The total light transmittance of the resin film of the present invention is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 88% or more, and most preferably 89% or more. A resin film having such a transmittance in such a range can be suitably used for, for example, a substrate for an image display device.

  When the resin film of the present invention is placed at 250 ° C. for 1.5 hours, the reduction rate of the total light transmittance is preferably 5% or less, more preferably 3% or less. With such a reduction rate, a practically acceptable light transmittance can be ensured even when subjected to high temperature treatment.

  The haze value of the 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 resin film of the present invention, discoloration (particularly yellowing) is suppressed even at high temperatures. When the resin film of the present invention is placed in air at 250 ° C. for 1.5 hours, the hue b value of the resin film is preferably 3 or less, more preferably 2 or less, and still more preferably 1. 5 or less, particularly preferably 1 or less. The hue b value is preferably closer to 0, and the lower limit of the hue b value is preferably 0.5, more preferably 0.2, and most preferably 0. The hue b value means a b value in Hunter's Lab color system.

  If the change in hue when the resin film of the present invention is heated from 25 ° C. to 250 ° C. in air is represented by the change in hue b value, the change in hue b value (absolute value) is preferably 2 or less. More preferably, it is 1 or less, More preferably, it is 0.5 or less. The change (absolute value) of the hue b value is preferably closer to 0, and the lower limit value of the change (absolute value) of the hue b value is preferably 0.5, more preferably 0.2, Most preferably 0. Since the resin film of the present invention is hardly yellowed, it can be suitably used for a substrate subjected to high temperature treatment.

B. Thermoplastic resin layer The total light transmittance of the thermoplastic resin layer is 85% or more, more preferably 86% or more, still more preferably 87% or more, and particularly preferably 88% or more. If it is such a range, the optical film which can be used suitably for the board | substrate for image display apparatuses can be obtained, for example. In the present invention, even in such a high transmittance thermoplastic resin layer, solvent cracks due to the curable resin composition for forming the curable resin layer hardly occur, and the curable resin layer Excellent adhesion.

  In the present invention, a thermoplastic resin layer that is difficult to yellow even at high temperatures is formed. When the thermoplastic resin layer is placed in air at 250 ° C. for 1.5 hours, the hue b value of the thermoplastic resin layer is preferably 3 or less, more preferably 2 or less, and still more preferably 1.5 or less, particularly preferably 1 or less. The hue b value is preferably closer to 0, and the lower limit of the hue b value is preferably 0.5, more preferably 0.2, and most preferably 0.

  If the change in hue when the resin layer is heated from 25 ° C. to 250 ° C. in air is represented by the change in hue b value, the change in hue b value (absolute value) is preferably 2 or less, Preferably it is 1.5 or less, More preferably, it is 1 or less. The change (absolute value) of the hue b value is preferably closer to 0, and the lower limit value of the change (absolute value) of the hue b value is preferably 0.5, more preferably 0.2, Most preferably 0. If such a thermoplastic resin layer is formed, a resin film that can be suitably used for a substrate subjected to high-temperature treatment can be obtained.

  The elastic modulus at 25 ° C. of the thermoplastic resin layer 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. If it is such a range, a resin film suitable as a resin film for glass reinforcement can be obtained. The elastic modulus in the present invention can be measured by dynamic viscoelastic spectrum measurement.

Fracture toughness value at 25 ° C. for the thermoplastic resin layer is preferably ^{1.5MPa · m 1/2 ~10MPa · m 1/2} , more preferably ^{2MPa · m 1/2 ~6MPa} · m 1/2 and particularly preferably from ^{2.5MPa · m 1/2 ~8MPa · m 1/2} . If it is such a range, a resin film suitable as a resin film for glass reinforcement can be obtained.

The refractive index (n _r ) at a wavelength of 550 nm of the thermoplastic resin layer is preferably 1.5 to 1.8.

  The thermoplastic resin forming the thermoplastic resin layer has a glass transition temperature of 250 ° C. or higher, preferably 250 ° C. to 500 ° C., more preferably 250 ° C. to 450 ° C., and further preferably 250 ° C. ~ 430 ° C. If a thermoplastic resin having a glass transition temperature in such a range is used, a thermoplastic resin layer having excellent heat resistance and hardly yellowing even at high temperatures can be formed.

  As the thermoplastic resin for forming the thermoplastic resin layer, any appropriate thermoplastic resin can be used as long as it can form a highly transparent and hardly yellowed thermoplastic resin layer as described above.

式（１）中、Ｒ^１は、炭素数１〜５の直鎖状もしくは分岐状のアルキル基であり、好ましくは炭素数１〜３の直鎖状もしくは分岐状のアルキル基であり、さらに好ましくはメチル基である。Ｒ^２は、炭素数２〜５の直鎖状もしくは分岐状のアルキル基であり、好ましくは炭素数が３または４の直鎖状もしくは分岐状のアルキル基であり、さらに好ましくはイソブチル基である。Ａ^１およびＡ^２はそれぞれ独立して上記一般式（３）〜（７）で表される連結基から選ばれる少なくとも１種であり、好ましくは一般式（３）または（４）で表される連結基である。Ｘ^１は、アリーレン基であり、好ましくは炭素数６〜１８の置換もしくは非置換のアリーレン基であり、より好ましくは炭素数６〜１２の置換もしくは非置換のアリーレン基である。Ｘ^１は、パラ位またはメタ位で連結基Ａ^２と連結基Ａ^１またはＡ^３とに連結する。
式（２）中、Ｒ^３は、メチル基またはアリール基であり、好ましくはメチル基または炭素数６〜１８の置換もしくは非置換のアリール基であり、さらに好ましくはメチル基または炭素数６〜１２の置換もしくは非置換のアリール基である。Ａ^３およびＡ^４はそれぞれ独立して、上記一般式（３）〜（７）で表される連結基から選ばれる少なくとも１種であり、好ましくは一般式（３）または（４）で表される連結基である。Ｘ^２は、アリーレン基であり、好ましくは炭素数６〜１８の置換もしくは非置換のアリーレン基であり、より好ましくは炭素数６〜１２の置換もしくは非置換のアリーレン基である。Ｘ^２は、パラ位またはメタ位で連結基Ａ^４と連結基Ａ^１またはＡ^３とに連結する。
Ｘ^１およびＸ^２の具体例としては、ベンゼン環、ナフタレン環、ビフェニル環等が挙げられる。 The thermoplastic resin preferably has a repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2). If a thermoplastic resin having such a repeating unit is used, a thermoplastic resin layer excellent in transparency, heat resistance and yellowing resistance can be formed. Moreover, if this thermoplastic resin is used, the thermoplastic resin layer excellent in toughness will be obtained, for example, the resin film suitable as a resin film for glass reinforcement can be obtained. Moreover, the 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 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.

式（８）中、Ｒ^４およびＲ^５は、好ましくは、それぞれ独立してメチル基または水素である。Ｂは、好ましくは炭素数４〜９の置換もしくは非置換のシクロアルカンまたは置換もしくは非置換のフルオレンであり、さらに好ましくは炭素数６〜９の置換もしくは非置換のシクロアルカンまたは置換もしくは非置換のフルオレンである。 Preferably, the thermoplastic resin further has a repeating unit represented by the following general formula (8). If the thermoplastic resin has such a repeating unit, a resin film excellent in yellowing resistance and 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 thermoplastic resin include (a) 4 ′-(1,3-dimethylbutylidene) bisphenol, 2,2-bis (4-hydroxyphenyl) -4-methyl-pentane, and 3,3-bis (4 -Hydroxyphenyl) pentane and 2,2-bis (4'-hydroxyphenyl) hexane at least one selected from the group consisting of (b) 4,4 '-(1-phenylethylidene) bisphenol, 4,4' At least one selected from the group consisting of-(1-phenylpropylidene) bisphenol, 4,4 '-(1-phenylpentylidene) bisphenol and 4,4'-(1-phenylhexylidene) bisphenol; ) From terephthalic acid chloride, isophthalic acid chloride, phthalic acid chloride and biphenyl dicarboxylic acid chloride The monomer composition containing at least one selected from the group 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 degree of polymerization of the thermoplastic resin is preferably 10 to 6000, more preferably 20 to 5000, and particularly preferably 50 to 4000.

The weight average molecular weight of the thermoplastic resin is preferably 2 × 10 ^{4 to} 100 × 10 ⁴ in terms of polystyrene, more preferably 8 × 10 ^{4 to} 100 × 10 ⁴ , and even more preferably 9 × 10 ^4. a to 50 × 10 ^4, particularly preferably ^{10 × 10 4 ~30 × 10 4} .

  The thermoplastic resin is preferably soluble in a solvent containing 50% or more of toluene and / or xylene, more preferably soluble in a solvent containing 70% or more of toluene and / or xylene, particularly preferably. It is soluble in a solvent containing 80% or more of toluene and / or xylene. If the thermoplastic resin is soluble in such a solvent, when the thermoplastic resin layer is obtained by coating, the coating can be easily performed.

  The thermoplastic resin layer 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.

  If necessary, various surface modification treatments may be performed on the surface of the thermoplastic resin layer on the curable resin layer side. As the surface modification treatment, any appropriate method is adopted depending on the purpose. For example, corona treatment, UV treatment or plasma treatment can be mentioned. When such a surface modification treatment is performed, a resin film having excellent adhesion between the thermoplastic resin layer and the curable resin layer can be obtained.

C. Curable resin layer In the resin film of the present invention, the curable resin layer is a layer that can function as a so-called hard coat layer, and is provided for imparting scratch resistance, heat resistance, solvent resistance, etc. to the resin film. . The curable resin layer is formed by using a curable resin composition containing a curable monomer and / or a curable oligomer, and curing the curable resin composition with, for example, heat or active energy rays. Can do.

  Examples of the curable monomer include epoxy monomers, oxetane monomers, acrylic monomers, thiol monomers, silicone monomers, and the like. As the epoxy monomer, an alicyclic epoxy monomer can be preferably used.

  Examples of the curable oligomer include silsesquioxane oligomers, epoxy oligomers, silicone oligomers, and acrylic oligomers.

  Preferably, the curable resin composition contains a silsesquioxane oligomer as a main component. The content ratio of the silsesquioxane oligomer in the curable resin composition is preferably 50% by weight or more, more preferably 60% by weight with respect to the total amount of the curable monomer and oligomer in the curable resin composition. % Or more, more preferably 70% by weight or more, particularly preferably 75% by weight or more, and most preferably 80% by weight to 95% by weight.

The silsesquioxane-based oligomer is composed of a Si—O bond in the main chain skeleton and a composition formula of (R—SiO _1.5 ) _n (R is any appropriate monovalent substituent; n is, for example, A siloxane-based compound represented by an integer of 6 or more, preferably an integer of 6 to 30, more preferably an integer of 6 to 16, and further preferably 6, 8 or 12. If the curable resin composition contains a silsesquioxane oligomer, a curable resin layer excellent in heat resistance and yellowing resistance can be formed. In addition, since the silsesquioxane oligomer can be a liquid having a relatively low viscosity, the content of the solvent in the curable resin composition can be reduced in each stage. If a curable resin composition having a small solvent content is used, the thermoplastic resin composition can be applied without causing solvent cracks. Furthermore, in the curable resin composition which has a silsesquioxane oligomer as a main component, the curing shrinkage is low. If such a curable resin composition is used, warping of the thermoplastic resin layer can be prevented, and when the resin film of the present invention is used in combination with thin glass, damage to the thin glass (cracks, Cracking, warping, etc.) can be reduced.

The silsesquioxane oligomers have various skeleton structures. Specifically, a random structure (the following formula (9)) in which (R-SiO _1.5 ) is randomly bonded, a ladder structure represented by the following formula (10), and a general formula (11) shown below. And a skeleton structure such as an incomplete cage structure represented by the following general formula (12). The silsesquioxane oligomer contained in the curable resin composition may have any structure, or may be a mixture of plural kinds of structures.

  Preferably, the curable resin composition includes at least a cage silsesquioxane-based oligomer. If a curable resin composition containing a cage silsesquioxane-based oligomer is used, a curable resin layer excellent in heat resistance and yellowing resistance can be formed. Further, the curable resin composition has a low curing shrinkage at each stage. In the present specification, the cage silsesquioxane oligomer means the above-mentioned silsesquioxane oligomer having a complete cage structure.

  The content ratio of the cage silsesquioxane oligomer is preferably 2 to 100 parts by weight, more preferably 100 parts by weight of the silsesquioxane oligomer in the curable resin composition. 2 to 98 parts by weight.

  The substituent R possessed by the silsesquioxane oligomer may be the same or different between units (between unit compositions). The silsesquioxane oligomer preferably has at least an oxetanyl group as the substituent R. If a curable resin composition containing a silsesquioxane oligomer having an oxetanyl group (particularly preferably, a cage silsesquioxane oligomer having an oxetanyl group) is used, a curable resin excellent in heat resistance and yellowing resistance A layer can be formed. Further, the curable resin composition has a low curing shrinkage at each stage. Examples of the substituent other than the oxetanyl group include a (meth) acryloyl group, a (meth) acrylate group, an epoxy group, a vinyl group, a carbonyl group, and a thiol group.

  In one embodiment, in the curable resin composition, an alicyclic epoxy monomer and / or an oxetane monomer is used in combination with the silsesquioxane oligomer. An alicyclic epoxy monomer and an oxetane monomer are preferable because of excellent compatibility with the silsesquioxane oligomer. If an alicyclic epoxy monomer or an oxetane monomer is contained, the curing rate and curing rate of the silsesquioxane oligomer can be increased.

  Specific examples of the alicyclic epoxy monomer include 3-glycidoxypropyltrimethoxysilane, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2,2-bis (hydroxymethyl) -1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol, ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy- Examples include 4-vinylcyclohexane, limonene dioxide, limonene monooxide, and side chain alicyclic epoxy-modified silicone oil.

  The content of the alicyclic epoxy monomer is preferably 1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight with respect to the total amount of the curable monomer and oligomer in the curable resin composition. %, More preferably 5 to 30% by weight.

  Specific examples of the oxetane monomer include 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl} oxetane, xylylenebisoxetane, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol). ), 2-ethylhexyl oxetane and the like.

  The content ratio of the oxetane monomer is preferably 0.5% by weight to 50% by weight, more preferably 1% by weight to 20% by weight with respect to the total amount of the curable monomer and oligomer in the curable resin composition. %, More preferably 3 to 10% by weight.

  The total content of the alicyclic epoxy monomer and the oxetane monomer is preferably 1% by weight to 50% by weight, more preferably 3%, based on the total amount of the curable monomer and oligomer in the curable resin composition. % By weight to 40% by weight, more preferably 5% by weight to 30% by weight. If it is such a range, it can be set as the curable resin composition which utilized the heat resistance of silsesquioxane, raising the cure rate and cure rate of silsesquioxane.

  The curable resin composition preferably contains a photocation generator. The photo cation generator means a compound that generates a cation species or a Lewis acid by an active energy ray (for example, visible light, ultraviolet ray, electron beam, etc.). If the said curable resin composition contains the photocation generator, sclerosis | hardenability will improve and it can form the curable resin layer which is excellent in solvent resistance, heat resistance, and scratch resistance.

  Examples of the photocation generator include sulfonium salt cation generators, iodonium salt cation generators, and the like. Examples of sulfonium salt cation generators include triphenylsulfonium hexafluoride antimony salt, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, bis- [4- (diphenylsulfonio) phenyl] sulfide-bis-hexa. Fluorophosphate, triarylsulfonium salt, 4-diphenylsulfoniodiphenyl sulfide hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate. Of these, 4-diphenylsulfoniodiphenyl sulfide hexafluoroantimonate is preferable. This is because of excellent heat resistance and excellent compatibility with curable monomers and oligomers.

  Examples of the iodonium salt-based cation generator include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, 4 -Isobutylphenyl (4-methylphenyl) iodonium, hexafluorophosphate, etc. are mentioned.

  Commercially available products of the sulfonium salt-based cation generator may be used as the above-mentioned photo cation generator, for example, trade names “SP-170”, “SP-150”, “SP” manufactured by Adeka Co., Ltd. -152 "; trade names" CPI101A "," CPI100P ", etc. manufactured by San Apro. Preferably, the trade name “CPI101A” manufactured by Sun Apro is used as the sulfonium salt-based cation generator. Examples of commercially available iodonium salt-based cation generators include trade name “Irgacure 250” manufactured by Ciba Japan.

  The content ratio of the photocation generator is preferably 1 part by weight to 3 parts by weight, more preferably 1 part by weight to 100 parts by weight of the total amount of the curable monomer and oligomer in the curable resin composition. 2 parts by weight.

  The curable resin composition preferably contains a thermal cation generator. The thermal cation generator means a compound that generates a cation species or a Lewis acid by heating (for example, 100 ° C. or higher). Examples of the thermal cation generator include aromatic sulfonium salts such as benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium salts, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, and amine imides.

  A commercially available product may be used as the thermal cation generator. Commercially available products of the thermal cation generator include trade names “Sun-Aid 60L”, “Sun-Aid 100L” and “Sun-Aid 150L” manufactured by Sanshin Chemical Co., Ltd. Among these, the trade name “Sun Aid 100L” is preferable in terms of pot life and reactivity.

  The content ratio of the thermal cation generator is preferably 1 part by weight to 5 parts by weight, more preferably 2 parts by weight with respect to 100 parts by weight of the total amount of the curable monomer and oligomer in the curable resin composition. 4 parts by weight.

  The content ratio of the thermal cation generator in the curable composition part is preferably larger than that of the photo cation generator. If the content ratio of the thermal cation generator is larger, the amount of the photo cation generator in the total amount of cation generator necessary for curing can be reduced. If the amount of the photocation generator is reduced, a curable resin layer with less coloring can be obtained.

  The curable composition may further contain a catalyst. Examples of the catalyst include a tin-based catalyst and a titanium-based catalyst. These catalysts are particularly useful when the curable resin composition contains a silsesquioxane oligomer. Examples of the tin-based catalyst include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, and bis (acetoxydibutyltin) oxide. Examples of the titanium-based catalyst include trade names “TA-25” and “TA-750” manufactured by Matsumoto Fine Chemical Co., Ltd. The content of the curing catalyst is preferably 0.01 to 3 parts by weight, more preferably 0.2 parts by weight with respect to 100 parts by weight of the total amount of the curable monomer and oligomer in the curable resin composition. It is -2 weight part, More preferably, it is 0.3 weight part-1 weight part. In the present specification, the “catalyst” refers to a catalyst other than the photo cation generator and the thermal cation generator and capable of functioning as a curing catalyst.

The storage elastic modulus at 30 ° C. of the curable resin layer is preferably 1 × 10 ⁸ Pa or more, more preferably 5 × 10 ⁸ Pa, further preferably 1 × 10 ⁹ Pa or more, and particularly preferably. Is 1 × 10 ⁹ Pa to 10 × 10 ⁹ Pa. If it is such a range, the resin film which is excellent in abrasion resistance, heat resistance, and solvent resistance can be obtained. In addition, the storage elastic modulus in this invention can be measured by dynamic viscoelastic spectrum measurement.

The storage elastic modulus at 250 ° C. of the curable resin layer is preferably 8 × 10 ⁷ Pa or more, more preferably 9 × 10 ⁷ Pa, further preferably 1 × 10 ⁸ Pa or more, and particularly preferably. Is 2 × 10 ⁸ Pa or more, particularly preferably 2 × 10 ⁸ Pa to 6 × 10 ⁹ Pa. If it is such a range, the resin film which was excellent in heat resistance and the yellowing was suppressed can be obtained. In addition, when applied to a substrate including glass, the glass can be prevented from being damaged under a wide range of temperatures.

  The storage elastic modulus at 250 ° C. of the curable resin layer is preferably 20% or more, more preferably 24% or more, and further preferably 25% or more with respect to the storage elastic modulus at 30 ° C., Particularly preferably, it is 30% or more. The ratio of the storage elastic modulus at 250 ° C. to the storage elastic modulus at 30 ° C. of the curable resin layer is preferably as high as possible, and the upper limit thereof is preferably 30%, more preferably 40%, still more preferably 60 %. In the present invention, a resin film that is excellent in heat resistance and suppressed in yellowing can be obtained by forming a curable resin layer in which the storage elastic modulus does not easily decrease even under heating. . Moreover, if the resin film of this invention is applied to the board | substrate provided with glass, damage of this glass can be prevented under wide temperature range.

  The elastic modulus at 25 ° C. of the curable resin layer 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. If it is such a range, the resin film suitable as a resin film for glass (especially thin glass) reinforcement can be obtained.

The fracture toughness value at 25 ° C. of the curable resin layer is preferably 1.5 MPa · m ^{1/2 to} 10 MPa · m ^1/2 , and more preferably 2 MPa · m ^{1/2 to} 6 MPa · m ^1/2. and particularly preferably from ^{2.5MPa · m 1/2 ~8MPa · m 1/2} . If it is such a range, the resin film suitable as a resin film for glass (especially thin glass) reinforcement can be obtained.

  The total light transmittance of the curable resin layer is 85% or more, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more. If it is such a range, the optical film which can be used suitably for the board | substrate for image display apparatuses can be obtained, for example.

  The hue b value when the curable resin layer is placed in an air atmosphere at 250 ° C. for 1.5 hours is preferably 3 or less, more preferably 2 or less, and further preferably −2 to 1. Particularly preferred is −1 to 0.5, and most preferred is 0. If such a curable resin layer is formed, a resin film that can be suitably used for a substrate subjected to high-temperature treatment can be obtained.

  The surface roughness Ra of the curable resin layer is preferably 100 nm or less, and more preferably 10 nm or less. In addition, in this specification, surface roughness Ra is arithmetic mean surface roughness Ra prescribed | regulated to JISB0601 (1994 edition).

D. Production Method of Resin Film The resin film of the present invention can be obtained by coating the curable resin composition on the thermoplastic resin layer.

  The thermoplastic resin layer can be formed, for example, by applying a thermoplastic resin composition. More specifically, the thermoplastic resin layer can be formed by applying a thermoplastic resin composition to any appropriate base material, and then drying the applied layer.

  The said thermoplastic resin composition contains the thermoplastic resin demonstrated by said B term, arbitrary appropriate solvents, and arbitrary appropriate additives as needed. Examples of the solvent include dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, toluene, anisole, tetrahydrofuran, xylene and the like. Of these, cyclopentanone or a mixed solvent of toluene / cyclopentanone is preferable. These solvents may be used alone or in a mixture at any appropriate ratio. As an additive contained in a thermoplastic resin composition, the additive demonstrated by the said B term may be used.

  Any appropriate method can be used as the method for applying the thermoplastic resin composition, for example, air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, casting. Coating methods such as coating, 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 offsets Examples of the printing method include a lithographic printing method such as a printing method, and a stencil printing method such as a screen printing method.

  Any appropriate drying method (for example, natural drying, air drying, heat drying) may be employed as a method for drying the coating layer of the thermoplastic resin composition. For example, in the case of heat drying, the drying temperature is typically 100 ° C. to 200 ° C., and the drying time is typically 1 minute to 30 minutes.

  After forming the thermoplastic resin layer, it is preferable to perform a surface modification treatment on the surface of the thermoplastic resin layer on the side where the curable resin layer is formed. Examples of the surface modification treatment include corona treatment, UV treatment, and plasma treatment.

  After forming the thermoplastic resin layer, the curable resin layer can be formed by applying the curable resin composition on the thermoplastic resin layer and then curing the curable resin composition. .

  As the curable resin composition, the curable resin composition described in the above section B can be used.

  The curable resin composition may further contain any appropriate solvent as necessary. Examples of the solvent include alcohol solvents and aliphatic hydrocarbon solvents.

  The curable resin composition has a solvent content of 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight, based on the total amount of the curable resin composition. It is as follows. More preferably, the curable resin composition does not contain a solvent. Thus, if a curable resin composition having a low solvent content or no solvent is used, solvent cracks that occur in the thermoplastic resin layer can be prevented.

  Any appropriate method can be used as a method of applying the curable resin composition. For example, the application methods mentioned as the application method of the thermoplastic resin composition can be used.

  Any appropriate method can be used as a method of curing the curable resin composition. Examples of the curing method include curing with heat, curing with active energy rays, and the like. You may use together hardening by a heat | fever and hardening by an active energy ray.

  When the curable resin composition is cured by heat, the heating temperature and the heating time can be set to any appropriate temperature depending on the characteristics of the curable resin in the curable resin composition. The heating temperature is preferably 150 ° C or higher, more preferably 150 ° C to 250 ° C, and further preferably 170 ° C to 220 ° C. The heating time is preferably 5 minutes to 1 hour, more preferably 10 minutes to 30 minutes.

  When the curable resin composition is cured by active energy rays, for example, visible light, ultraviolet rays, electron beams and the like are used as the active energy rays. Preferably, ultraviolet rays are used as active energy rays.

Irradiation conditions for ultraviolet light irradiation in ultraviolet curing can be set to any appropriate conditions according to the characteristics of the curable resin in the curable resin composition. Typically, the irradiation integrated light quantity is 100 mJ / cm ^{2 to} 2000 mJ / cm ² and the irradiation time is 5 minutes to 30 minutes.

  Preferably, when the curable resin composition is cured, a smooth sheet is brought into contact with the curable resin composition. More specifically, a smooth sheet is disposed on the surface of the coating layer formed by applying the curable resin composition on the side opposite to the thermoplastic resin layer, and then subjected to a curing treatment to obtain a curable resin. A layer may be formed. Thus, if the curable resin composition is cured, a resin film excellent in smoothness can be obtained. In addition, you may peel the said sheet | seat arrange | positioned on the application layer of curable resin composition in the middle of a hardening process. Moreover, you may harden a curable resin composition in the state which sandwiched the laminated body of a thermoplastic resin layer and the application layer of a curable resin composition with two sheets using two sheets. The surface roughness Ra of the sheet is preferably 100 nm or less. The total light transmittance of the sheet is preferably 80% or more.

E. Transparent substrate In one embodiment of the present invention, a transparent substrate is provided. The transparent substrate includes inorganic glass and the resin film disposed on one or both sides of the inorganic glass.

  As the resin film used for the transparent substrate, the resin film described in the items A to D can be used. Preferably, the resin film is disposed such that the thermoplastic resin layer is on the inorganic glass side.

  The thickness of the inorganic glass used for the transparent substrate 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 the present invention, by disposing a resin film on one side or both sides of the inorganic glass, the inorganic glass can be prevented from cracking, cracking, warping, and the like. Moreover, since inorganic glass can be protected in this way, the thickness of inorganic glass can be made thin.

  When the said resin layer is arrange | positioned on both surfaces of the said inorganic glass, the thickness of each resin film may be the same and may differ. Preferably, the thickness of each resin film is the same. Furthermore, each resin film may be the same type of resin film or a different type of resin film. Preferably, the same type of resin film is used. Therefore, most preferably, each resin film is comprised so that it may become the same thickness with the same kind of resin film. 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.

E-1. 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 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.

E-2. 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.

E-3. Manufacturing method of transparent substrate The transparent substrate can be obtained by forming the resin film of the present invention including the thermoplastic resin layer and the curable resin layer on the inorganic glass by any appropriate method.

  In one embodiment, the inorganic glass is used as a base material, and a thermoplastic resin composition is formed on the inorganic glass to form a thermoplastic resin layer, and then curable on the thermoplastic resin layer. A transparent substrate can be obtained by forming the resin layer. The method for applying the thermoplastic resin composition (application method, drying method) and the method for forming the curable resin layer are as described in the above section D.

  In another embodiment, a thermoplastic resin film is bonded to inorganic glass to form a thermoplastic resin layer, and then a curable resin layer is formed on the thermoplastic resin layer to obtain a transparent substrate. be able to. The thermoplastic resin film can be formed on another substrate by applying the thermoplastic resin composition as described in the above section D. The thermoplastic resin film and the inorganic glass can be attached with any appropriate adhesive or pressure-sensitive adhesive. The method for forming the curable resin layer is as described in the above section D.

  Before the thermoplastic resin composition is applied, or before the thermoplastic resin film is attached, the surface of the inorganic glass that contacts the thermoplastic resin layer may be subjected to a coupling treatment. If the inorganic glass is subjected to a coupling treatment, a transparent substrate having excellent adhesion between the thermoplastic resin layer and the inorganic glass can be obtained.

  Examples of the coupling agent used for the coupling treatment include an epoxy terminal coupling agent, an amino group-containing coupling agent, a methacrylic group-containing coupling agent, and a thiol group-containing coupling agent.

  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.

  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) Yellowing resistance The yellowing resistance of the formed thermoplastic resin layer was evaluated.
The yellowing resistance of the thermoplastic resin layer is determined by placing the inorganic glass / thermoplastic resin layer laminate (b value before heating: 0) before forming the curable resin layer at 250 ° C. for 1.5 hours, The b value in the color system of the hunter of the transparent substrate was measured and evaluated.
The b value was measured using a high-speed integrating sphere type spectral transmittance measuring device “DOT-3C” manufactured by Murakami Color Research Laboratory.
(2) Change in storage elastic modulus of curable resin layer The storage elastic modulus at 30 ° C. and the storage elastic modulus at 250 ° C. of the curable resin layer were measured using a dynamic viscoelasticity measuring device DMA (manufactured by TA Instruments). did. By pulling a film-like sample (width: 10 mm, length: 100 mm) while heating, the storage elastic modulus at each temperature was measured. In this evaluation, a curable resin layer similar to the curable resin layer formed on the thermoplastic resin layer was prepared as a single sample, and the storage elastic modulus was measured for the single curable resin layer. . The change in storage elastic modulus (%) was calculated by (storage elastic modulus at 250 ° C.) / (Storage elastic modulus at 30 ° C.) × 100.
(3) Transparency The transparency of the obtained transparent substrate was evaluated by measuring the total light transmittance (550 nm) with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100).
(4) Adhesiveness of curable resin layer The adhesiveness of the curable resin layer was evaluated by a cross-cut peel test of JIS K 5400. That is, a cut is made with a cutter at intervals of 1 mm in a 10 mm square on the surface of the obtained transparent substrate on the side of the curable resin layer, 100 grids are made, and an adhesive tape is attached thereon, and then peeled off. The adhesiveness was evaluated based on the number of grids of the resin layer that did not peel from the thermoplastic resin layer.
(5) Heat resistance On the curable resin layer of the obtained transparent substrate, an indium-zinc oxide (IZO) layer having a thickness of 100 nm was formed by sputtering. The heat resistance was evaluated from the state after the transparent substrate with the IZO layer was heated at 230 ° C. for 15 minutes.
(6) Solvent resistance The obtained transparent substrate was immersed in acetone, subjected to ultrasonic treatment for 30 minutes, and the state of the curable resin layer was visually confirmed.

[Production Example 1] Preparation of thermoplastic resin composition In a reaction vessel equipped with a stirrer, 7.65 g (0.028 mol) of 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'- 12.35 g (0.043 mol) of (1-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 a white thermoplastic resin A. The glass transition temperature of the thermoplastic resin A was 273 ° C.
The thermoplastic resin A and a toluene / cyclopentanone mixed solvent (weight ratio 8: 2) are mixed to prepare a toluene / cyclopentanone solution of thermoplastic resin A (thermoplastic resin concentration: 9% by weight). Thus, a thermoplastic resin composition was obtained.

[Production Example 2] Preparation of curable resin composition a Silsesquioxane-based oligomer having an oxetanyl group (manufactured by Toa Gosei Co., Ltd., trade name “OX-SQ TX-100”), and having an oxetanyl group And 3 parts by weight of a silsesquioxane-based oligomer (trade name “OX-SQ SI-20”, manufactured by Toagosei Co., Ltd.) having a structural unit derived from polydimethylsiloxane in a part of the skeleton, and 3 ′, 4 ′ -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, trade name “Celoxide 2021”) 1.5 parts by weight and 3-ethyl-3 {[(3-ethyloxetane-3-yl) Methoxy] methyl} oxetane (trade name “Aron oxetane 221”, manufactured by Toa Gosei Co., Ltd.) and 3-glycidoxypropyltrimethoxysilane 0.4 parts by weight from Shin-Etsu Chemical Co., Ltd., trade name “KBM403”) and 0.1 weight by weight of 4-diphenylsulfoniodiphenyl sulfide hexafluoroantimonate (trade name “CPI101A” from Sun Apro) as a photocation generator. And 0.2 parts by weight of an aromatic sulfonium antimonate (trade name “Sun Aid 100L” manufactured by Sanshin Chemical Co., Ltd.) as a thermal cation generator and 0.05 part by weight of dibutyltin dilaurate as a curing catalyst Then, a curable resin composition a was obtained.

[Production Example 3] Preparation of curable resin composition b A curable resin composition b was obtained in the same manner as in Production Example 2 except that dibutyltin dilaurate as a curing catalyst was not added.

[Production Example 4] Preparation of curable resin composition c 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, trade name “Celoxide 2021”) and 2 parts by weight , 2-bis (hydroxymethyl) -1-butanol, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (manufactured by Daicel, trade name “EHPE3150”), 4 parts by weight, 3-ethyl-3 { 2 parts by weight of [(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name “Aronoxetane 221” manufactured by Toagosei Co., Ltd.) and 4-diphenylsulfoniodiphenyl sulfide hexafluoro as a photocation generator 0.1 part by weight of antimonate (trade name “CPI101A” manufactured by San Apro Co., Ltd.), a thermal cation generator, A mixture of 0.2 part by weight of all aromatic sulfonium antimonates (trade name “SANAID 100L” manufactured by Sanshin Chemical Co., Ltd.) and 0.05 parts by weight of dibutyltin dilaurate as a curing catalyst, c was obtained.

[Production Example 5] Preparation of curable resin composition d Silsesquioxane oligomer having oxetanyl group (manufactured by Toa Gosei Co., Ltd., trade name "OX-SQ TX-100") 5 parts by weight, and having oxetanyl group In place of 3 parts by weight of a silsesquioxane oligomer having a structural unit derived from polydimethylsiloxane in a part of the skeleton (product name “OX-SQ SI-20” manufactured by Toa Gosei Co., Ltd.) Having 8 parts by weight of a silsesquioxane oligomer (manufactured by Toa Gosei Co., Ltd., trade name “AC-SQ TA-100”), and 4-diphenylsulfoniodiphenyl sulfide hexafluoroantimonate (Sanpro) as a photocation generator. 2-hydroxy-2-methyl-1-pheny as a radical generator instead of 0.1 part by weight - propan-1-one except for using (Ciba Chemicals Inc., trade name "DAROCURE1173") 0.4 parts by weight, in the same manner as in Preparation Example 1 to obtain a curable resin composition d.

[Example 1]
The thermoplastic resin composition obtained in Production Example 1 is applied to one side of an inorganic glass whose surface is corona-treated, and is dried at 100 ° C. for 10 minutes, and an inorganic glass (thickness: 50 μm) and a thermoplastic resin layer (thickness). : 27 μm, total light transmittance 89%) was obtained.
From the inorganic glass, the thermoplastic resin layer, and the coating layer of the curable resin composition, the curable resin composition a obtained in Production Example 2 is applied on the thermoplastic resin layer of the laminate (1). Thus obtained laminate (2) was obtained.
The laminate (2) is sandwiched between sheets made of two cycloolefins (manufactured by Zeon Corporation, trade name “Zeonor ZF16”), and laminated / rolled with a sheet / inorganic glass / thermoplastic resin layer / A laminate (3) composed of a coating layer / sheet of the curable resin composition was formed.
Thereafter, the coating layer of the curable resin composition was irradiated with ultraviolet rays (365 nm, integrated light amount: 1000 mJ). Subsequently, after peeling the said sheet | seat, it heated further at 180 degreeC for 20 minute (s), the curable resin composition was hardened, and the curable resin layer (thickness: 9 micrometers) was formed.
By the above operation, a transparent substrate composed of inorganic glass / thermoplastic resin layer / curable resin layer was obtained.

[Example 2]
A transparent substrate was obtained in the same manner as in Example 1 except that the curable resin composition b obtained in Production Example 3 was used in place of the curable resin composition a.

[Comparative Example 1]
A transparent substrate was obtained in the same manner as in Example 1 except that the curable resin composition c obtained in Production Example 4 was used in place of the curable resin composition a.

[Comparative Example 2]
Example 1 except that a thermoplastic resin layer formed from polyethersulfone (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumika Excel PES5003PS”, glass transition temperature: 220 ° C.) is formed as the thermoplastic resin layer. Similarly, a transparent substrate was obtained.

  As is clear from Table 1, according to the present invention, a resin film excellent in heat resistance and yellowing resistance can be provided. Moreover, the resin film of this invention is excellent also in transparency and the adhesiveness of a thermoplastic resin layer and a curable resin composition layer by providing the curable resin layer formed from specific curable resin.

  The 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 Thermoplastic resin layer 11 Curable resin layer 100 Resin film

Claims (12)

A thermoplastic resin layer formed from a thermoplastic resin, and a curable resin layer disposed on the thermoplastic resin layer,
The glass transition temperature of the thermoplastic resin is 250 ° C. or higher,
The total light transmittance of the thermoplastic resin layer is 85% or more;
The hue change when the thermoplastic resin layer is heated in air from 25 ° C. to 250 ° C. is 2 or less in hue b value,
The curable resin layer is formed by curing a curable resin composition containing a curable monomer and / or a curable oligomer,
The solvent content in the curable resin composition is 1% by weight or less based on the total amount of the curable resin composition,
The storage elastic modulus at 250 ° C. of the curable resin layer is 20% or more with respect to the storage elastic modulus at 30 ° C.,
Resin film.   The resin film according to claim 1, wherein a hue change when heated from 25 ° C. to 250 ° C. is 2 or less in terms of a hue b value.   The resin according to claim 1 or 2, wherein a surface of the thermoplastic resin layer on a side of the curable resin layer is subjected to a surface modification treatment, and the surface modification treatment is a corona treatment, a UV treatment, or a plasma treatment. the film.   The resin film according to claim 1, wherein the curable resin layer is a layer obtained by curing the curable resin composition with active energy rays.   The resin film according to any one of claims 1 to 3, wherein the curable resin layer is a layer obtained by curing the curable resin composition at a temperature of 150 ° C or higher.   The curable resin layer is a layer formed by bringing a sheet having a surface roughness Ra of 100 nm or less into contact with the curable resin composition when the curable resin composition is cured. The resin film in any one.   The resin film according to claim 1, wherein the curable resin composition contains a cage-type silsesquioxane-based oligomer.   The resin film according to claim 7, wherein the cage silsesquioxane-based oligomer has an oxetanyl group.   The resin film according to any one of claims 1 to 8, wherein the curable resin composition contains an alicyclic epoxy monomer. The curable resin composition further comprises a photo cation generator and a thermal cation generator,
The content ratio of the photocation generator is 1 part by weight to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable monomer and the curable oligomer in the curable resin composition,
The content ratio of the thermal cation generator is 1 part by weight to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable monomer and the curable oligomer in the curable resin composition.
The resin film according to claim 1.   The resin film according to claim 10, wherein the curable resin composition has a content of the thermal cation generator larger than a content ratio of the photo cation generator. A transparent substrate provided with inorganic glass and the resin film in any one of Claims 1-11 arrange | positioned at the single side | surface or both surfaces of this inorganic glass.

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