JP2006089651A - Coating liquid for forming anchor layer, substrate having barrier property and method for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating liquid for forming an anchor layer and having a good coating aptitude on a specific plastic substrate excellent in heat resistance and dimensional stability, and having a low linear expansion coefficient, and also capable of forming an anchor layer excellent in bonding property with a plastic, metal, metal oxide. etc., and a substrate having the barrier property, e.g. useful for an organic EL display, etc., and excellent in close adhesion with a plastic substrate, an inorganic film such as a metal, metal oxide, etc., and having a good barrier property against oxygen or steam. <P>SOLUTION: This coating liquid containing an anchoring agent obtained by polymerizing a silane-modified epoxy resin expressed by chemical formula (1) [wherein, R<SP>a</SP>to R<SP>e</SP>are each methyl or ethyl and may be the same or different] is characterized by having within 5-60 % range ring opening ratio of the glycidyl groups of the anchoring agent-forming coating liquid, based on the silane-modified epoxy resin measured by an infrared spectrometry. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is, for example, an anchor layer forming coating solution using a silane-modified epoxy resin that can be used for a barrier substrate used in an organic electroluminescent display device and the like, and formed using the same. The present invention relates to a barrier substrate having an anchor layer, and a method for producing the same.

  Conventional epoxy resin-based compositions have been widely used in applications such as various coating agents, adhesives, and sealing agents because of their relatively excellent water resistance, adhesion, and chemical resistance. However, in recent years, as the epoxy resin-based composition is applied to a display device having a member vulnerable to oxygen or water vapor, such as an organic electroluminescent (hereinafter, abbreviated as EL) display device, the epoxy resin is used. The required level of adhesion, heat resistance, transparency, and the like of a resin film obtained using a system composition to a substrate such as glass, metal, or plastic has increased.

  In order to satisfy such a requirement, for example, Patent Document 1 is used as a coating agent or an adhesive excellent in heat resistance, solvent resistance, adhesion to a substrate such as glass, metal or plastic, and weather resistance. Silane-modified epoxy resin compositions have been proposed. The resin film obtained using this silane-modified epoxy resin has the advantage of being excellent in adhesion to a substrate such as glass, metal or plastic, heat resistance and transparency. However, depending on the type of substrate, there is a problem that the coating suitability of the silane-modified epoxy resin composition is poor.

  In recent years, the use of plastic base materials has been studied along with the reduction in thickness and weight of display devices. In addition to surface smoothness and transparency, this plastic base material can withstand the heat during display manufacturing. A high level of heat resistance is required. Moreover, high dimensional stability and low linear expansion coefficient are also required.

  For such plastic substrates with excellent heat resistance, good dimensional stability, and low linear expansion coefficient, the application suitability of the above silane-modified epoxy resin composition may be poor, and it is applicable to barrier substrates. When it did, there existed a problem that barrier property fell.

JP 2002-226770 A

  The present invention has been made in view of the above-mentioned problems, has excellent heat resistance and dimensional stability, has good applicability to a specific plastic base material having a low coefficient of linear expansion, and is made of plastic and metal. It can be used for an anchor layer forming coating solution that can form an anchor layer with excellent adhesion to metal and metal oxides, and for example, an organic EL display device, etc. The main object is to provide a barrier substrate having excellent adhesion to an inorganic film and good barrier properties against oxygen and water vapor.

  In order to achieve the above object, the present invention contains an anchor agent obtained by polymerizing a silane-modified epoxy resin represented by the following chemical formula (1), and measures the above silane-modified epoxy resin measured by infrared spectroscopy. Provided is a coating liquid for forming an anchor layer, wherein the ratio of ring opening of the glycidyl group of the anchoring agent is in the range of 5% to 60%.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  According to the present invention, by containing the anchor agent obtained by polymerizing the silane-modified epoxy resin and ring-opening reaction of the glycidyl group within a predetermined range, a specific plastic substrate excellent in heat resistance and dimensional stability can be obtained. Thus, the coating suitability of the anchor layer forming coating solution can be improved. Further, since the silane-modified epoxy resin as described above is used, there is an advantage that the adhesion between the plastic substrate and an inorganic film such as a metal or metal oxide is good.

  The anchor layer forming coating solution preferably contains an epoxy curing agent and a silane curing catalyst. This is because it is preferable to use an epoxy curing agent and a silane curing catalyst when polymerizing the silane-modified epoxy resin.

  The anchor layer-forming coating solution preferably has a viscosity in the range of 5 mPa · s to 100 mPa · s at 25 ° C. It is because the coating suitability with respect to a specific plastic base material can be made favorable by making the viscosity of the coating liquid for anchor layer formation into the said range.

  The present invention also provides a polycarbonate resin substrate obtained by irradiating a polycarbonate resin film obtained by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group with ionizing radiation, and the above polycarbonate resin substrate. A barrier substrate having an anchor layer formed on the anchor layer and a deposited film formed on the anchor layer, wherein the anchor layer is a cured product of a silane-modified epoxy resin represented by the following chemical formula (1) A barrier substrate is provided.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  According to the present invention, by using the above bisphenol compound and further irradiating with ionizing radiation, it is possible to obtain a polycarbonate resin substrate having excellent heat resistance, good dimensional stability, and low linear expansion coefficient. The anchor layer, which is a cured product of the silane-modified epoxy resin, has good adhesion to such a polycarbonate-based resin substrate, and also has excellent adhesion to the deposited film. Therefore, the barrier substrate of the present invention can obtain good barrier properties against water vapor and oxygen.

  In the said invention, it is preferable that the linear expansion coefficient of the said anchor layer is 100 ppm / degrees C or less in 50 to 150 degreeC. This is because, when the linear expansion coefficient is in the above range, the anchor layer can be prevented from peeling, distorting, and the like.

  In the present invention, the total light transmittance of the anchor layer is preferably 80% or more. This is because, when the barrier substrate of the present invention is used in an organic EL display device, for example, when light is extracted from the barrier substrate side, the total light transmittance is preferably in the above range.

  Furthermore, in this invention, the said bisphenol compound may be shown by following Chemical formula (2), and may be shown by following Chemical formula (3).

Here, in formula (2), R ¹ and R ² are independently of each other hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms, X is carbon, m is 4 or 5, R ³ and R ⁴ are independently selected for each X, and are independently hydrogen or carbon An alkyl group having a number of 1 to 6 is shown, and R ³ and R ⁴ simultaneously represent an alkyl group on at least one X atom.
In formula (3), R ^{5 to} R ⁸ are hydrogen, or an alkyl group, aralkyl group or alkoxy group having 1 to 7 carbon atoms, and each of R ^{5 to} R ⁸ may be the same or different.
By using such a bisphenol compound, the glass transition temperature (Tg) can be made relatively high, and the heat resistance can be further improved.

  Furthermore, the present invention provides the above-described barrier substrate, the first electrode layer formed on the barrier substrate, the organic EL layer formed on the first electrode layer and including at least a light emitting layer, and the organic EL An organic EL display device comprising: a second electrode layer formed on the layer.

  According to the present invention, since the above-described barrier substrate is used, it has a good barrier property against oxygen and water vapor, and the generation of dark spots can be suppressed. Thereby, it can be set as the organic EL display device in which a favorable image display is possible.

  Further, the present invention provides an anchor layer forming coating solution characterized by adjusting a coating solution for forming an anchor layer by subjecting a part of the glycidyl group of the silane-modified epoxy resin represented by the following chemical formula (1) to a ring-opening reaction. A method for producing a working fluid is provided.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  According to the present invention, by applying a ring-opening reaction to a part of the glycidyl group of the silane-modified epoxy resin, it is possible to improve the coating suitability for a specific plastic substrate. Moreover, the anchor layer formed using the coating liquid for forming an anchor layer of the present invention has an advantage of high adhesion to a plastic substrate and an inorganic film such as a metal or metal oxide.

  In the said invention, it is preferable to ring-open the glycidyl group of the said silane modified epoxy resin within the range of 5%-60% by the said ring-opening reaction. This is because, by setting the ratio of ring opening of the glycidyl group within the above range, it is possible to improve the coating suitability of the coating liquid for forming an anchor layer with respect to a specific plastic substrate.

  In the ring-opening reaction, it is preferable to use an epoxy curing agent and a silane curing catalyst.

The present invention also forms a polycarbonate resin film by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group, and forms a polycarbonate resin substrate by irradiating the polycarbonate resin film with ionizing radiation. A polycarbonate resin substrate forming step;
An anchor layer forming step of forming an anchor layer by applying and curing the anchor layer forming coating solution obtained by the above-described method for producing an anchor layer forming coating solution on the polycarbonate resin substrate;
And a vapor deposition film forming step of forming a vapor deposition film on the anchor layer.

  According to the present invention, the heat resistance can be improved by using the bisphenol compound, and the dimensional stability and the linear expansion coefficient can be improved by irradiating the polycarbonate resin film with ionizing radiation. it can. For this reason, it is possible to obtain a polycarbonate resin substrate having excellent heat resistance, good dimensional stability, and a low linear expansion coefficient. Moreover, it is possible to easily produce a continuous sheet-like polycarbonate resin substrate. Furthermore, since the anchor layer is formed using the above-described anchor layer forming coating solution, the coating suitability to the polycarbonate resin substrate is good, and the adhesion between the polycarbonate resin substrate and the deposited film is good. Can be increased. Further, the formation of the anchor layer can smooth the surface of the polycarbonate resin substrate, and a dense vapor deposition film can be formed. Therefore, it is possible to obtain a barrier substrate having a good barrier property against oxygen and water vapor.

  In the said invention, the said bisphenol compound may be shown by following Chemical formula (2), and may be shown by following Chemical formula (3).

Here, in formula (2), R ¹ and R ² are independently of each other hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms, X is carbon, m is 4 or 5, R ³ and R ⁴ are independently selected for each X, and are independently hydrogen or carbon An alkyl group having a number of 1 to 6 is shown, and R ³ and R ⁴ simultaneously represent an alkyl group on at least one X atom.
In the formula ^(3), R 5 ~R ⁸ is hydrogen or an alkyl group having 1 to 7 carbon atoms, an aralkyl group or alkoxy ^group, each of R 5 to R ⁸ may be the same or different.

  Furthermore, in the present invention, it is preferable that the ionizing radiation is irradiated in a deoxygenated atmosphere in the polycarbonate resin substrate forming step. This is because the ionizing radiation is irradiated in a deoxygenated atmosphere, so that it is possible to avoid suppression of crosslinking by oxygen.

  Under the present circumstances, it is preferable to perform the said irradiation of ionizing radiation under a heating in the said polycarbonate-type resin base material formation process. This is because the irradiation with ionizing radiation is performed in a deoxygenated atmosphere under heating, so that it is possible to promote improvement in dimensional stability, in particular, reduction in linear expansion coefficient.

  In the present invention, it is preferable to perform heating in a deoxygenated atmosphere after the ionizing radiation irradiation in the polycarbonate resin base material forming step. This is because heating in a deoxygenated atmosphere is performed after the irradiation with ionizing radiation, so that it is possible to further improve the dimensional stability, in particular, to further reduce the linear expansion coefficient.

  In the present invention, a coating for forming an anchor layer is applied to a specific plastic substrate having excellent heat resistance and dimensional stability by polymerizing a silane-modified epoxy resin and ring-opening reaction of glycidyl groups within a predetermined range. There is an effect that the application suitability of the liquid can be improved. Moreover, this anchor layer forming coating solution has an advantage of good adhesion to a plastic substrate and an inorganic film such as a metal or metal oxide. By using such a coating solution for forming an anchor layer, it is possible to form an anchor layer suitable for a barrier substrate used in, for example, an organic EL display device.

  Hereinafter, the anchor layer forming coating solution, the barrier substrate, and the organic EL display device using the same will be described in detail. Furthermore, the manufacturing method of the coating liquid for anchor layer formation and a barrier property board | substrate is demonstrated.

A. First, the anchor layer forming coating solution of the present invention will be described. The anchor layer-forming coating solution of the present invention contains an anchor agent obtained by polymerizing a silane-modified epoxy resin represented by the following chemical formula (1), and the above-described silane-modified epoxy resin measured by infrared spectroscopy. The ratio of the ring opening of the glycidyl group of the anchor agent is in the range of 5% to 60%.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  According to the present invention, by containing the anchor agent obtained by polymerizing the silane-modified epoxy resin and ring-opening reaction of the glycidyl group within a predetermined range, a plastic substrate excellent in heat resistance and dimensional stability, particularly described below. The coating suitability of the anchor layer forming coating solution can be improved with respect to the polycarbonate-based resin base material described in the section “B. Barrier Substrate”. In general, it is considered that when a silane-modified epoxy resin is polymerized, the viscosity of the coating liquid is increased, so that the coating suitability is impaired. However, in the present invention, a part of the glycidyl group is subjected to a ring-opening reaction to some extent, By polymerizing the epoxy resin, the coating suitability can be improved. This is presumably because the affinity between the glycidyl group of the silane-modified epoxy resin and the specific polycarbonate resin is low. On the other hand, if the ratio of ring opening of glycidyl group is increased, sol-gel reaction of silane-modified epoxy resin may occur along with ring opening reaction of glycidyl group. Will be inferior. Therefore, in the present invention, the ratio of ring opening of the glycidyl group of the anchor agent to the silane-modified epoxy resin is set within a predetermined range.

  The anchor agent used in the present invention has a ratio of ring opening of the glycidyl group of the anchor agent to the silane-modified epoxy resin measured by infrared spectroscopy within a range of 5% to 60%, preferably 10%. It is preferable to be in the range of -55%. This is because if the ratio of the ring opening of the glycidyl group of the anchor agent is too small, uneven coating may occur when the anchor layer forming coating solution of the present invention is applied to a specific polycarbonate resin substrate. . On the other hand, if the ratio of ring opening of the glycidyl group of the anchor agent is too large, as described above, the viscosity of the coating liquid for forming the anchor layer increases due to the progress of the sol-gel reaction of the silane-modified epoxy resin, and the coating suitability deteriorates. Because there is.

In addition, the ratio of the ring opening of the glycidyl group is measured as follows. That is, first, in the infrared absorption spectrum, the intensity of the absorption band (near 1510 cm ⁻¹ ) derived from the benzene ring of bisphenol A is defined as 100, and the intensity of the absorption band (near 920 cm ⁻¹ ) derived from the glycidyl group before and after polymerization. Measure each. When the intensity of the absorption band derived from the glycidyl group before polymerization measured in this way is A, and the intensity of the absorption band derived from the glycidyl group after polymerization is B,
(AB) / A × 100 (%)
The value represented by is the ratio of ring opening of the glycidyl group. The infrared absorption spectrum was measured using a 610 type infrared spectrophotometer manufactured by JASCO Corporation.

The anchor layer forming coating solution of the present invention preferably contains an epoxy curing agent and a silane curing catalyst. This is because the anchor agent used in the present invention is obtained by polymerizing the silane-modified epoxy resin represented by the chemical formula (1). When the silane-modified epoxy resin is polymerized, the epoxy curing agent and the silane curing agent are used. This is because it is preferable to use a catalyst.
Hereinafter, each structure of such an anchor layer forming coating solution will be described.

1. Anchor Agent The anchor agent used in the present invention is obtained by polymerizing the silane-modified epoxy resin represented by the chemical formula (1).
Hereinafter, a method for producing a silane-modified epoxy resin and an anchor agent will be described.

(1) Silane-modified epoxy resin The silane-modified epoxy resin used in the present invention is represented by the above chemical formula (1). Here, in the above formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different. Moreover, the average value of the repeating unit number a is 0.3 to 5.8, and the average value of the repeating unit number b is 2 to 7.

Such a silane-modified epoxy resin can be obtained by subjecting a bisphenol type epoxy resin and an alkoxysilane partial condensate to a dealcoholization condensation reaction. A method for producing a silane-modified epoxy resin is described in JP-A No. 2002-226770.
Moreover, as a commercial item of the silane modified epoxy resin, Composeran E (trade name, manufactured by Arakawa Chemical Industries, Ltd.) and the like can be mentioned.

(2) Method for producing anchor agent In the present invention, the anchor agent can be prepared by subjecting a part of the glycidyl group of the silane-modified epoxy resin to a ring-opening reaction.

  The reaction temperature is not particularly limited as long as it is a temperature at which the glycidyl group can be opened in a predetermined range by a ring-opening reaction. The reaction temperature varies depending on the type and content of the epoxy curing agent and silane curing catalyst described later, the reaction time described later, and is usually about 50 ° C to 150 ° C, preferably in the range of 70 ° C to 120 ° C. It is.

  Further, the reaction time is not particularly limited as long as it is a time during which the glycidyl group can be ring-opened within a predetermined range by a ring-opening reaction, as described above. The reaction time varies depending on the type and content of the epoxy curing agent and silane curing catalyst described later, the above reaction temperature, etc., but is usually about 1 minute to 2 hours, preferably in the range of 10 minutes to 1 hour. It is.

  The viscosity of the coating solution for forming an anchor layer thus obtained is particularly limited as long as the viscosity is good for coating with respect to a specific plastic substrate, particularly a specific polycarbonate resin substrate. It is not a thing. In addition, the viscosity of the anchor layer forming coating solution varies depending on the type and content of the epoxy curing agent described later, but specifically, the viscosity at 25 ° C. is in the range of 5 mPa · s to 100 mPa · s. Yes, preferably in the range of 10 mPa · s to 50 mPa · s.

2. Epoxy curing agent In the present invention, an epoxy curing agent is used to promote the ring-opening reaction of the glycidyl group of the silane-modified epoxy resin.

As an epoxy hardener, what is normally used as a hardener of an epoxy resin can be used. For example, a novolak resin curing agent, an imidazole curing agent, an acid anhydride curing agent, or the like can be used. Specifically, examples of the novolak resin-based curing agent include phenol novolac resin, bisphenol novolac resin, and poly p-vinylphenol. Examples of imidazole curing agents include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium. -Trimellitate, 2-phenylimidazolium isocyanurate, etc. are mentioned. Furthermore, as the acid anhydride curing agent, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylene Examples include tetrahydrophthalic anhydride and methyl-3,6-endomethylenetetrahydrophthalic anhydride. Furthermore, curing agents such as dicyandiamide and ketimine compounds can be used.
Among these, considering the reactivity of the epoxy curing agent and the coating suitability of the anchor layer forming coating solution, it is preferable to use a novolac resin-based curing agent, particularly a phenol novolac resin.

  The content of the epoxy curing agent varies depending on the type of the epoxy curing agent, but in the case of a novolak resin-based curing agent, when the anchor agent is produced, 5 parts by weight with respect to 100 parts by weight of the silane-modified epoxy resin. Within the range of -60 parts by weight, preferably within the range of 10-30 parts by weight. This is because if the content of the novolak resin-based curing agent is too small, the ring-opening reaction of the glycidyl group may not proceed appropriately. On the other hand, when the content of the novolac resin-based curing agent is too large, the anchor layer obtained may become yellow when the anchor layer is formed using the anchor layer forming coating solution of the present invention, and the organic EL This is because it becomes difficult to apply to a member requiring transparency, such as an anchor layer of a barrier substrate used in a display device or the like.

  Further, in the case of an imidazole-based curing agent or an acid anhydride-based curing agent, when producing the anchor agent, it is within the range of 10 to 50 parts by weight, preferably 15 with respect to 100 parts by weight of the silane-modified epoxy resin. It is preferably contained within a range of ˜30 parts by weight. This is because if the content of the imidazole curing agent or the acid anhydride curing agent is too small, the ring opening reaction of the glycidyl group may not proceed appropriately. On the other hand, if the content of the imidazole-based curing agent or the acid anhydride-based curing agent is too large, the reactivity becomes fast and it may be difficult to adjust the viscosity of the anchor layer forming coating solution.

  Further, in order to promote the ring-opening reaction of the glycidyl group, a curing accelerator can be contained in addition to the epoxy curing agent. Examples of such a curing accelerator include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl). Tertiary amines such as phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine Organic phosphines such as phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetrafe Such as tetraphenyl boron salts such as Ruboreto can be mentioned.

  The curing accelerator may be contained in the range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the silane-modified epoxy resin when the anchor agent is produced.

3. Silane curing catalyst In the present invention, a silane curing catalyst is used to promote the sol-gel reaction at the alkoxysilane site of the silane-modified epoxy resin.

  As the silane curing catalyst, a general catalyst such as an acid or basic catalyst or a metal catalyst can be used. Examples thereof include organic metal salts such as sodium acetate and lithium acetate. Further, tin octylate and dibutyltin dilaurate are preferable because of high activity and excellent solubility.

  The content of the silane curing catalyst is appropriately selected depending on the activity of the silane curing catalyst used and the type of the epoxy curing agent. Usually, a silane curing catalyst is contained in the range of 10 to 50 parts by weight, preferably in the range of 15 to 30 parts by weight with respect to 100 parts by weight of the silane-modified epoxy resin when the anchor agent is produced. The

4). Others In the present invention, when preparing the anchor agent, the silane-modified epoxy resin or the like may be dissolved or dispersed in a solvent. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, or a mixed solvent thereof can be used.

  The said solvent is normally mix | blended so that solid content concentration, such as the said silane modified epoxy resin, may be about 0.5 to 20 weight%.

  Moreover, in order to adjust the coating liquid for anchor layer formation of this invention to the viscosity and density | concentration suitable for application | coating, the said solvent can also be used.

  Furthermore, the anchor layer forming coating solution of the present invention is a filler, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, and the like, as long as the effects of the present invention are not impaired. You may contain an antibacterial agent, an antifungal agent, a leveling agent, an antifoamer, a coloring agent, a stabilizer, a coupling agent, etc.

B. Next, the barrier substrate of the present invention will be described.
The barrier substrate of the present invention comprises a polycarbonate resin substrate obtained by irradiating a polycarbonate resin film obtained by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group with ionizing radiation, and the polycarbonate resin group. A barrier substrate having an anchor layer formed on a material and a deposited film formed on the anchor layer, wherein the anchor layer is a cured product of a silane-modified epoxy resin represented by the following chemical formula (1) It is characterized by being.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  FIG. 1 is a schematic sectional view showing an example of the barrier substrate of the present invention. In the barrier substrate of the present invention, an anchor layer 2 and a vapor deposition film 3 are formed in this order on a polycarbonate resin substrate 1.

  The polycarbonate-based resin base material in the present invention is excellent in heat resistance because it uses the above-described bisphenol compound, and for example, a heating process or an organic EL display device in producing an organic EL display device using the barrier substrate of the present invention. Even when exposed to an increase in temperature during use, it is unlikely to deteriorate or deteriorate. Moreover, since a polycarbonate-type resin base material is obtained by irradiating with ionizing radiation, it is excellent in the dimensional stability with respect to a temperature change, has a low coefficient of linear expansion, and hardly causes peeling or distortion.

In the present invention, by using the cured product of the silane-modified epoxy resin as an anchor layer, it is possible to obtain an anchor layer having high adhesion to the polycarbonate-based resin base material having the above-described characteristics, and further vapor deposition. Adhesiveness with the film can also be good. For this reason, it can be set as the barrier property board | substrate with high barrier property with respect to water vapor | steam and oxygen.
Hereinafter, each configuration of such a barrier substrate will be described.

1. Anchor layer The anchor layer used in the present invention is formed on a polycarbonate-based resin substrate described later, and is a cured product of a silane-modified epoxy resin represented by the above chemical formula (1).

  The anchor layer has a linear expansion coefficient at 50 ° C. to 150 ° C. of 100 ppm / ° C. or less, preferably 80 ppm / ° C. or less. This is because, when the linear expansion coefficient is in the above range, the anchor layer can be prevented from peeling, distorting, and the like.

  The linear expansion coefficient is a value measured by using a thermomechanical analyzer TMA8310 manufactured by Rigaku Denshi Co., Ltd. and increasing the temperature at a rate of 1 g load and 3 ° C./min.

  Further, the total light transmittance of the anchor layer is preferably 80% or more, more preferably 90% or more. This is because, when the barrier substrate of the present invention is used in an organic EL display device, for example, when light is extracted from the barrier substrate side, the total light transmittance is preferably in the above range.

  In addition, the said total light transmittance is an average value of the value measured using Shimadzu Corporation Corp. UV-3100 within the wavelength range of 380 nm-800 nm.

  The thickness of the anchor layer is not particularly limited as long as the above-described properties can be satisfied. Specifically, it can be set at about 0.01 μm to 5 μm, preferably 0.01 μm to 2 μm. Within range. This is because if the anchor layer is too thin, the adhesion to the polycarbonate-based resin substrate or the vapor deposition film may be insufficient, or distortion may occur easily. On the other hand, if the anchor layer is too thick, cracks may occur when the anchor layer is formed. Moreover, it may turn yellow depending on the type of epoxy curing agent used to form the anchor layer, and when the barrier substrate of the present invention is used in, for example, an organic EL display device, the anchor layer must be transparent. This is because it becomes difficult to apply.

  The anchor layer used in the present invention is preferably formed using the above-described anchor layer forming coating solution. This is because, as described above, the anchor layer forming coating solution has an advantage of good coating suitability for a polycarbonate-based resin substrate described later. Thereby, since generation | occurrence | production of the application | coating nonuniformity of the said anchor layer formation coating liquid can be suppressed, barrier property can be improved.

  The silane-modified epoxy resin is the same as that described in the above-mentioned section “A. Anchor layer forming coating solution 1. Anchor agent”, and the anchor layer forming method is described later in “E. Barrier”. The description is omitted here since it is described in the section “Method for manufacturing a conductive substrate”.

2. Polycarbonate resin substrate The polycarbonate resin substrate used in the present invention is obtained by irradiating a polycarbonate resin film obtained by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group with ionizing radiation. .

  Specifically as a bisphenol compound used in order to obtain a polycarbonate-type resin base material, what is shown by following Chemical formula (2) or following Chemical formula (3) is mentioned.

Here, in formula (2), R ¹ and R ² are independently of each other hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms, X is carbon, m is 4 or 5, R ³ and R ⁴ are independently selected for each X, and are independently hydrogen or carbon An alkyl group having a number of 1 to 6 is shown, and R ³ and R ⁴ simultaneously represent an alkyl group on at least one X atom.

Here, in formula (3), R ^{5 to} R ⁸ are hydrogen, or an alkyl group having 1 to 7 carbon atoms, an aralkyl group, or an alkoxy group, and each of R ^{5 to} R ⁸ may be the same or different.

  Examples of the bisphenol compound represented by the chemical formula (2) include 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3, Mention may be made of 3-dimethyl-cyclohexane or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane. Among these, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane is particularly preferable. Also, one or more of these can be selected and used.

  As described above, the bisphenol compound represented by the chemical formula (2) may be used alone, or may be used in combination with a bisphenol compound other than the bisphenol compound represented by the chemical formula (2). Examples of bisphenol compounds that can be used in combination with the bisphenol compound represented by the chemical formula (2) include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxy). Phenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, and 1,1-bis (4 -Hydroxyphenyl) cyclohexane.

  On the other hand, as the bisphenol compound represented by the chemical formula (3), for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dimethylphenyl) fluorene or 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene can be mentioned. Of these, 9,9-bis (4-hydroxyphenyl) fluorene is particularly preferred. Also, one or more of these can be selected and used.

  As described above, the bisphenol compound represented by the chemical formula (3) may be used alone, or may be used in combination with a bisphenol compound other than the bisphenol compound represented by the chemical formula (2). Examples of bisphenol compounds that can be used in combination with the bisphenol compound represented by the chemical formula (3) include bis (4-hydroxyphenyl) methane [commonly known as bisphenol F], 1,1-bis (4-hydroxyphenyl) ethane, , 2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenyl sulfone [commonly known as bisphenol S], Alternatively, bisphenols such as 4,4-dihydroxydiphenyl sulfide and 4,4-dihydroxybiphenol can be mentioned.

  Furthermore, bisphenol compounds represented by the following chemical formulas (4) to (10) can also be used.

Here, R ^{5 to} R ⁸ in the chemical formulas (4) to (8) are the same as those in the chemical formula (3), and Me in the chemical formulas (9) and (10) represents a methyl group. .

  The above bisphenol compounds can be used alone or in combination of two or more, and can also be used in combination with other bisphenol compounds.

  The polycarbonate resin substrate used in the present invention can be obtained by irradiating the polycarbonate resin film formed by polymerizing the bisphenol compound with ionizing radiation. This polycarbonate resin film is obtained by polymerizing the above bisphenol compound by a conventional method of transesterification or phosgene method to obtain a polycarbonate resin, and then using the obtained polycarbonate resin by a melt extrusion method or a casting method. A film can be formed. In the present invention, before receiving irradiation with ionizing radiation, a polycarbonate resin film is prepared as a long continuous sheet, and irradiation with ionizing radiation described later is performed while the continuous sheet (polycarbonate resin film) is running. Therefore, finally, a long continuous sheet-like polycarbonate resin substrate can be obtained.

  When an organic EL display device is formed using the barrier substrate of the present invention, if unevenness exists in the barrier substrate, unevenness in thickness occurs in the organic EL layer, resulting in uneven light emission. It is preferable to use a belt having improved smoothness as the casting belt at the time. At this time, it is preferable to form a polycarbonate resin film by a casting method.

  The thickness of the polycarbonate resin film is preferably 50 μm to 500 μm.

  In addition, since the polycarbonate-based resin film uses a bisphenol compound having an aliphatic cyclic hydrocarbon group as a raw material, in particular, compared with a raw material made from bisphenol A in which a portion to which two hydroxyphenols adhere is propane, The glass transition temperature (Tg) can be improved. Thereby, heat resistance can be improved. Furthermore, the characteristics of the polycarbonate resin film can be improved, and in particular, the dimensional stability and the coefficient of linear expansion can be improved.

Examples of ionizing radiation that can be used include ultraviolet rays, electron beams, γ rays, α rays, neutron rays, and X rays. However, the ionizing action of ionizing polycarbonate resin membranes is the permeability to polycarbonate resin membranes. From the viewpoint of ease of handling, and electron beam by an electron beam accelerator or gamma ray by cobalt 60 are preferable, and an electron beam is particularly preferable.
The irradiation amount of ionizing radiation is about 1 Gy to 5 Gy, and the acceleration voltage of the electron beam is about 0.1 MeV to 5 MeV. In addition, ultraviolet rays are also preferable because the apparatus is small and relatively simple, and there is no problem such as shielding.

  In the present invention, when the polycarbonate resin film is irradiated with ionizing radiation, the dimensional stability is improved, and in particular, the linear expansion coefficient is lowered. Therefore, the polycarbonate is suitable for use as a substrate of a liquid crystal display device or an organic EL display device. A resin base material can be obtained. Generally, when a polycarbonate resin film is irradiated with ionizing radiation, a bond in a polymer chain may be broken or a cross-link between polymers may occur. However, the polycarbonate resin film used in the present invention Since it is derived from the raw material and has high heat resistance, it is considered that cross-linking occurs preferentially.

  Irradiation with ionizing radiation can be performed in air, but in order to avoid the above-mentioned crosslinking being suppressed by the presence of oxygen in the air, the irradiation with ionizing radiation is performed in a deoxygenated atmosphere, for example, in nitrogen or an inert gas. It is preferably carried out in a vacuum or in a vacuum.

  The polycarbonate resin film is preferably irradiated with ionizing radiation under heating. This is because irradiation with ionizing radiation under heating promotes improvement in dimensional stability, in particular, reduction in the linear expansion coefficient. Furthermore, the polycarbonate resin film is preferably in a deoxygenated atmosphere, for example, in nitrogen or an inert gas, rather than in the air when irradiated with ionizing radiation.

  In the present invention, it is preferable to further heat after irradiating the polycarbonate resin film with ionizing radiation, and it is preferable to heat in a deoxygenated atmosphere. This is because the internal strain can be further relaxed by this heating, and the dimensional stability can be further improved, in particular, the linear expansion coefficient can be further reduced.

3. Vapor Deposition Film The vapor deposition film used in the present invention is formed on the anchor layer and has a barrier property against oxygen and water vapor. As a vapor deposition film used in the present invention, a vapor deposition film generally used as a barrier layer for an organic EL display device or the like can be used. In addition, when the barrier substrate of the present invention is used in an organic EL display device, the vapor deposition film needs to have transparency when extracting light from the barrier substrate side.

  Examples of the material used for such a deposited film include inorganic oxides such as silicon oxide, silicon oxynitride, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, magnesium oxide, tin oxide, and indium oxide alloy; silicon nitride, Inorganic nitrides such as aluminum nitride, titanium nitride, and silicon carbonitride; metals such as aluminum, silver, tin, chromium, nickel, and titanium;

  Among the above materials, silicon oxide or silicon oxynitride is preferable. This is because these materials have good adhesion to the anchor layer. Such a silicon oxide thin film can be formed using an organosilicon compound as a raw material. Specific examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propylsilane. , Phenylsilane, vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like. Among the organosilicon compounds, tetramethoxysilane (TMOS) and hexamethyldisiloxane (HMDSO) are preferably used. This is because these are excellent in handleability and vapor deposition film characteristics.

  The vapor deposition film may be a single layer, or a plurality of layers may be laminated in order to improve barrier properties. Moreover, as a combination in the case of stacking, the same kind or different kinds may be used.

  The film thickness of such a vapor deposition film is not particularly limited as long as it has a barrier property against water vapor and oxygen and transparency, and is appropriately selected depending on the above-described materials. Usually, it is in the range of 5 nm to 5000 nm, preferably in the range of 50 nm to 1000 nm, particularly preferably in the range of 100 nm to 500 nm. Further, when aluminum oxide or silicon oxide is used, it is more preferably in the range of 10 nm to 300 nm. When the film thickness of the deposited film is too thin, the barrier property is reduced. On the other hand, when the film thickness of the deposited film is too thick, cracks may occur when forming the deposited film, and the transparency may be lowered. Because.

  The vapor deposition film can be formed by physical vapor deposition (PVD) such as sputtering, vapor deposition, or ion plating, chemical vapor deposition (CVD), or the like. Among these, chemical vapor deposition is effective in that the effect of heat on the polycarbonate resin substrate and anchor layer during the formation of the deposited film can be made relatively small, the production rate is high, and a uniform thin film can be easily obtained. The method (CVD) is preferred.

4). Overcoat layer In this invention, as shown in FIG. 2, for example, the overcoat layer 4 may be formed on the vapor deposition film 3. This is because the barrier property against oxygen and water vapor can be improved by covering the deposited film with the overcoat layer. In general, in a deposited film, a portion having a low density may be generated between crystals in the process of crystal growth, whereby microscopic defects exist, and the barrier property may be lowered by the defects. In the present invention, even if a microscopic defect exists in the vapor deposition film, the microscopic defect portion of the vapor deposition film is compensated by covering the vapor deposition film with an overcoat layer made of a resin having a high barrier property. Therefore, it is considered that the barrier property is improved.

  The material used for the overcoat layer is not particularly limited as long as it has the above-described properties. For example, an epoxy resin having two epoxy groups in one molecule (hereinafter referred to as “polyfunctional epoxy resin”). The thermosetting resin containing “.” Is preferably used. An overcoat layer formed by curing a thermosetting resin containing a polyfunctional epoxy resin has a high barrier property and is excellent in transparency and heat resistance. This is because there is an advantage that even if it is exposed to a temperature rise during use, it is difficult to cause alteration or deterioration such as discoloration or a decrease in barrier properties. In addition, such an overcoat layer is excellent in adhesion to the vapor deposition film and dimensional stability against heating or temperature change, hardly causes peeling or distortion, and further has an effect of preventing peeling or cracking of the vapor deposition film. Because there is. Since the polycarbonate resin substrate has flexibility, it can be made flexible. In such a case, the effect of preventing peeling, distortion, cracking, etc. of the overcoat layer or the deposited film is particularly advantageous.

  Moreover, the thermosetting resin containing a polyfunctional epoxy resin becomes a coating film (thermosetting resin film) having appropriate adhesiveness that can be transferred to another surface to be transferred when coated on a support. Has the advantage. For this reason, it is not a method of directly applying a thermosetting resin containing a polyfunctional epoxy resin on a vapor deposition film, but a method of transferring after forming a coating film (thermosetting resin film) on another support beforehand. The overcoat layer can be formed by laminating on the deposited film and curing it. In such a method of transferring the thermosetting resin film onto the vapor deposition film, there is no possibility that the vapor deposition film is damaged by the solvent contained in the thermosetting resin. Further, since the overcoat layer can be formed on the vapor deposition film without using a coating machine, the vapor deposition film does not come into contact with a member such as a head of the coating machine and is not damaged. Therefore, the barrier property can be improved as compared with the case where the thermosetting resin is directly applied onto the deposited film.

Furthermore, since the surface of the overcoat layer has the same smoothness as the support of the transfer body, the smoothness is higher than that formed by directly applying the thermosetting resin on the vapor deposition film. Get higher. Thereby, when it is set as an organic electroluminescent display apparatus using the barrier substrate of this invention, for example, since a thin electrode layer becomes difficult to be destroyed, generation | occurrence | production of a dark spot can be prevented.
As described above, the thermosetting resin containing the polyfunctional epoxy resin is very suitable as an overcoat layer for covering the deposited film.

  Examples of the polyfunctional epoxy resin used in the present invention include pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl). ) Isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like can be used.

  In particular, as a polyfunctional epoxy resin having good transferability, it is preferable to use a high molecular weight polyfunctional epoxy (that is, having two or more epoxy groups) polymer. In order to obtain a high molecular weight epoxy polymer, for example, a two-stage method is used in which a bifunctional epoxy resin and a bifunctional phenol are used as raw materials, and an etherification catalyst is used to alternately polymerize in a synthetic reaction solvent. It is preferable. The bifunctional epoxy resin, which is a raw material for synthesizing the high molecular weight epoxy polymer, is not particularly limited as long as it is a compound having two epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, other diglycidyl etherified products of bifunctional phenols, bifunctional alcohols Examples thereof include diglycidyl etherified products, halides thereof, hydrogenated products, and the like. The molecular weights of these compounds are not limited, and they may have two epoxy groups in the molecule even if they are polymerized with each other. Moreover, several types of these compounds can be used in combination. Furthermore, components other than the bifunctional epoxy resin may be included.

  The bifunctional phenols that are the raw materials for synthesizing the high molecular weight epoxy polymer are not particularly limited as long as they are compounds having two phenolic hydroxyl groups. For example, hydroquinone, resorcinol, catechol, which are monocyclic bifunctional phenols, bisphenol A, bisphenol F, biphenol, dihydroxydiphenyl ether, dihydroxydiphenyl sulfone, and their halides, alkyl group substitution products, isomers, etc., which are polycyclic bifunctional phenols There is. The molecular weights of these compounds are not limited, and they may have two phenolic hydroxyl groups in the molecule even when they are polymerized with each other or with other compounds. Several types of these compounds can be used in combination. Moreover, you may contain components other than bifunctional phenols.

  The molecular weight and viscosity of the polyfunctional epoxy resin affect the film formability and tackiness of the thermosetting resin containing it, and change the transferability of the thermosetting resin film provided on the transfer body. It is preferable to adjust to such a range. From this viewpoint, the weight average molecular weight in terms of polystyrene of the polyfunctional epoxy resin is preferably in the range of 10,000 to 500,000, particularly preferably in the range of 50,000 to 300,000. The viscosity of the polyfunctional epoxy resin is preferably in the range of 1 to 50 Pa · s, particularly preferably in the range of 5 to 30 Pa · s.

  Although a thermosetting resin may consist only of a polyfunctional epoxy resin, you may mix | blend other components, such as a hardening | curing agent, with a polyfunctional epoxy resin as needed. Curing agents can be used by appropriately selecting from those conventionally blended in epoxy resins, such as acid anhydride curing agents, polyamine curing agents, polyphenol curing agents, catalytic curing agents, etc. A curing agent can be used.

  Specific examples of the acid anhydride curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phthalic anhydride, anhydrous Aromatic polycarboxylic acid anhydrides such as trimellitic acid can be mentioned.

  The amount of the polyfunctional epoxy resin in the thermosetting resin is not particularly limited, but is usually blended in the thermosetting resin at a ratio of about 80% by weight.

Further, the thermosetting resin may be dissolved or dispersed using a solvent and adjusted to a concentration suitable for coating. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, or a mixed solvent thereof can be used.
The overcoat layer-forming coating solution containing a thermosetting resin is usually adjusted so that the solid content concentration is about 10 to 50% by weight.

The thermosetting resin can be applied onto the transfer body by a general method such as a roll coater, a gravure coater, a knife coater, or a dip coater.
Then, the obtained thermosetting resin film is dried by heating to a temperature at which no thermosetting reaction occurs, for example, a temperature range of 50 to 100 ° C. At this time, the thickness of the thermosetting resin film is adjusted in consideration of the thickness of the overcoat layer to be finally formed.

The overcoat layer used in the present invention is formed as follows.
That is, if the vapor deposition film of the polycarbonate resin base material on which the anchor layer and the vapor deposition film are formed and the thermosetting resin film of the transfer body face each other, the thermosetting resin film has adhesiveness. Adhere to the deposited film. When the support of the transfer body is pulled in this state, the thermosetting resin film remains on the deposited film, and the support is peeled off. In this way, the thermosetting resin film is transferred onto the vapor deposition film.
Since the thermosetting resin film adheres to the vapor deposition film by its own adhesive force, the thermosetting resin film is usually obtained by dry lamination of the polycarbonate resin substrate on which the anchor layer and the vapor deposition film are formed and the transfer body. Can be transferred. Further, if necessary, an adhesive may be thinly applied on the thermosetting resin film or the vapor deposition film, and the thermosetting resin film may be transferred by wet lamination. At this time, when the polycarbonate resin base material on which the anchor layer and the vapor deposition film are formed and the transfer body are overlapped with each other, the transfer property of the thermosetting resin film ′ can be improved by applying a suitable pressure. Also, depending on the material of the support used for the transfer body, thermosetting is possible even with pressure that is lightly pressed with a finger after the polycarbonate resin base material on which the anchor layer and vapor deposition film are formed and the transfer body are superimposed. The photosensitive resin film can be sufficiently transferred onto the deposited film.
The overcoat layer can be formed by thermosetting the thermosetting resin film thus transferred onto the vapor deposition film. The thermosetting resin film can be cured under a general temperature condition for curing a thermosetting resin containing an epoxy resin. Specifically, thermosetting can be performed by heating in the range of about 120 to 180 ° C. for 5 minutes to 1 hour using a heating means such as an oven.

5. Others In the present invention, the deposited film and the overcoat layer may be formed twice or more alternately. This is because particularly excellent barrier properties can be obtained. In addition, when the vapor deposition film and the overcoat layer are alternately provided, the adhesion between the layers is good, and therefore, unlike the case where the vapor deposition film is formed thick or overlapped, peeling and cracking are unlikely to occur. In the case where the vapor deposition film and the overcoat layer are provided in an overlapping manner, a sufficient barrier property is usually obtained by repeating about 2 to 4 layers.

As the barrier property of the barrier substrate of the present invention, the oxygen gas permeability (OTR) is preferably 1 cc / m ² / day / atm or less, more preferably 0.5 cc / m ² / day / atm or less, In particular, it is preferably 0.1 cc / m ² / day / atm or less. Further, the water vapor transmission rate (WVTR) is preferably 1 g / m ² / day or less, more preferably 0.5 g / m ² / day or less, and particularly preferably 0.1 g / m ² / day or less. When the oxygen gas permeability and the water vapor permeability are in the above-described ranges, the barrier property of the present invention can be increased, and the barrier substrate of the present invention can be applied to an organic EL display device having a member weak against oxygen or water vapor. It is because it can be used suitably.

  The oxygen permeability is a value measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% Rh. is there. The water vapor transmission rate is a value measured using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. It is.

  The barrier substrate of the present invention can be applied to a display substrate and a display device. For example, a color filter substrate can be obtained by forming red, green and blue color filter layers on a barrier substrate so as to have a predetermined arrangement. Further, for example, a display substrate can be obtained by forming a thin film such as ITO (indium tin oxide) on a barrier substrate and patterning by a photolithography method as necessary to form a transparent electrode layer. Furthermore, the barrier substrate of the present invention can be applied to organic EL display devices and liquid crystal display devices. Among these, it is suitably used for an organic EL display device having a member vulnerable to oxygen and water vapor.

C. Organic EL Display Device Next, the organic EL display device of the present invention will be described. An organic EL display device of the present invention includes the above-described barrier substrate, a first electrode layer formed on the barrier substrate, an organic EL layer formed on the first electrode layer and including at least a light emitting layer, And a second electrode layer formed on the organic EL layer.

According to the present invention, since the above-described barrier substrate is used, it has a barrier property against oxygen and water vapor, and the generation of dark spots can be suppressed. Therefore, an organic EL display device capable of displaying a good image can be obtained.
Hereinafter, each configuration of such an organic EL display device will be described.

1. Organic EL Layer The organic EL layer used in the present invention is composed of one or more organic layers including at least a light emitting layer. That is, the organic EL layer is a layer including at least a light emitting layer, and the layer configuration is a layer having one or more organic layers. Usually, when an organic EL layer is formed by a wet method by coating, it is often difficult to stack a large number of layers in relation to a solvent, so that it is often formed of one or two organic layers. However, it is possible to further increase the number of layers by devising an organic material so that the solubility in a solvent is different or by combining a vacuum deposition method.

Examples of the organic layer formed in the organic EL layer other than the light emitting layer include charge injection layers such as a hole injection layer and an electron injection layer. Furthermore, examples of the other organic layers include a charge transport layer such as a hole transport layer that transports holes to the light-emitting layer and an electron transport layer that transports electrons to the light-emitting layer. In many cases, it is formed integrally with the charge injection layer by imparting a charge transporting function. In addition, as an organic layer formed in the organic EL layer, it prevents holes or electrons from penetrating like a carrier block layer and further prevents diffusion of excitons and confines excitons in the light emitting layer. And a layer for increasing the recombination efficiency.
Hereinafter, each structure of such an organic EL layer will be described.

(1) Light emitting layer The light emitting layer used in the present invention has a function of emitting light by providing a recombination field of electrons and holes. As the material for forming the light emitting layer, a dye-based light-emitting material, a metal complex-based light-emitting material, or a polymer-based light-emitting material can be generally used.

  Examples of dye-based light emitting materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine rings Examples thereof include compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, coumarin derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

Metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, iridium metal complex, platinum metal complex, etc. The metal has Al, Zn, Be, Ir, Pt, etc., or a rare earth metal such as Tb, Eu, Dy, etc., and the ligand has an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, etc. A metal complex etc. can be mentioned. Specifically, tris (8-quinolinol) aluminum complex (Alq ₃ ) can be used.

  Furthermore, as the polymer light emitting material, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, polydialkylfluorene derivatives, And copolymers thereof. Moreover, what polymerized the said pigment-type luminescent material and metal complex type | system | group luminescent material is also mentioned.

  Among the above, the light emitting material used in the present invention is preferably a metal complex light emitting material or a polymer light emitting material, and more preferably a polymer light emitting material. Of the polymer light emitting materials, a conductive polymer having a π-conjugated structure is preferable. Examples of the conductive polymer having such a π-conjugated structure include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives as described above. , Polydialkylfluorene derivatives, and copolymers thereof.

  The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination field between electrons and holes, and can be, for example, about 1 nm to 200 nm. .

  Further, a dopant that emits fluorescence or phosphorescence may be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, fluorene derivatives, and the like. Can be mentioned.

  The method for forming the light emitting layer is not particularly limited as long as it is a method capable of high-definition patterning. For example, vapor deposition method, printing method, inkjet method, spin coating method, casting method, dipping method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, and self-assembly method (Alternate adsorption method, self-assembled monolayer method) and the like. Among these, it is preferable to use a vapor deposition method, a spin coating method, and an ink jet method. Further, when the light emitting layer is patterned, it may be applied separately by a masking method for pixels having different light emission colors, or a partition may be formed between the light emitting layers. As a material for forming such a partition, a photocurable resin such as a photosensitive polyimide resin or an acrylic resin, a thermosetting resin, an inorganic material, or the like can be used. Furthermore, you may perform the process which changes the surface energy (wetting property) of the material which forms these partition walls.

(2) Charge injection / transport layer In the present invention, a charge injection / transport layer may be formed between the first electrode layer and the light emitting layer, or between the light emitting layer and the second electrode layer. The charge injecting and transporting layer here has a function of stably transporting charges from the first electrode layer or the second electrode layer to the light emitting layer, and the charge injecting and transporting layer is used as the first electrode. By providing between the light-emitting layer and the light-emitting layer or between the light-emitting layer and the second electrode layer, the injection of charges into the light-emitting layer is stabilized, and the light emission efficiency can be increased.

  Examples of the charge injection transport layer include a hole injection transport layer that transports holes injected from the anode into the light emitting layer, and an electron injection transport layer that transports electrons injected from the cathode into the light emitting layer. Hereinafter, the hole injection / transport layer and the electron injection / transport layer will be described.

(I) Hole Injecting and Transporting Layer The hole injecting and transporting layer used in the present invention is either a hole injecting layer for injecting holes into the light emitting layer or a hole transporting layer for transporting holes. The hole injection layer and the hole transport layer may be laminated, or a single layer having both the hole injection function and the hole transport function may be used.

  The material used for the hole injecting and transporting layer is not particularly limited as long as it can stably transport holes injected from the anode into the light emitting layer. In addition to the exemplified compounds, phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, polythiophene, polyphenylene vinylene derivatives, etc. may be used. it can. Specifically, bis (N- (1-naphthyl-N-phenyl) benzidine (α-NPD), 4,4,4-tris (3-methylphenylphenylamino) triphenylamine (MTDATA), poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS), polyvinyl carbazole (PVCz), etc. are mentioned.

  The thickness of the hole injecting and transporting layer is not particularly limited as long as the hole injecting holes from the anode and transporting the holes to the light emitting layer is sufficiently exhibited. It is preferable to be in the range of 5 nm to 1000 nm, especially in the range of 10 nm to 500 nm.

(Ii) Electron Injection / Transport Layer The electron injection / transport layer used in the present invention may be either an electron injection layer for injecting electrons into the light emitting layer or an electron transport layer for transporting electrons. A layer and an electron transport layer may be laminated, or a single layer having both an electron injection function and an electron transport function may be used.

  The material used for the electron injection layer is not particularly limited as long as the material can stabilize the injection of electrons into the light emitting layer. In addition to the compounds exemplified as the light emitting material of the light emitting layer, Aluminum lithium alloy, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium fluoride, barium fluoride, aluminum oxide, strontium oxide, calcium, polymethyl methacrylate, sodium polystyrene sulfonate, lithium, cesium, Alkali metals, alkali metal halides, alkali metal organic complexes, and the like, such as cesium fluoride, can be used.

  In addition, the thickness of the electron injection layer is not particularly limited as long as the electron injection function is sufficiently exerted.

On the other hand, the material used for the electron transport layer is not particularly limited as long as it is a material capable of transporting electrons injected from the first electrode layer or the second electrode layer into the light emitting layer. Examples include bathocuproin, bathophenanthroline, phenanthroline derivative, triazole derivative, oxadiazole derivative, or tris (8-quinolinol) aluminum complex (Alq ₃ ).

  Furthermore, as an electron injecting and transporting layer composed of a single layer having both an electron injecting function and an electron transporting function, a metal doped layer in which an alkali metal or an alkaline earth metal is doped on an electron transporting organic material is formed. This can be used as an electron injecting and transporting layer. Examples of the electron-transporting organic material include bathocuproin, bathophenanthroline, and phenanthroline derivatives. Examples of the metal to be doped include Li, Cs, Ba, and Sr.

2. First electrode layer and second electrode layer The first electrode layer and the second electrode layer used in the present invention may be an anode or a cathode as long as they are opposed to each other. Moreover, although it may or may not have transparency, it is appropriately selected depending on the light extraction surface or the light reception surface. For example, when light is extracted from the first electrode layer side, the first electrode layer needs to be transparent or translucent.

  As the anode, it is preferable to use a conductive material having a high work function so that holes can be easily injected. Specifically, a metal having a high work function such as ITO, indium oxide, gold, polyaniline, polyacetylene, polyalkyl, etc. Examples thereof include conductive polymers such as thiophene derivatives and polysilane derivatives.

  On the other hand, as the cathode, it is preferable to use a conductive material having a small work function so that electrons can be easily injected. Examples thereof include magnesium alloys such as MgAg, aluminum alloys such as AlLi, AlCa, and AlMg, and Li and Ca. Examples include alkali metals and alkaline earth metals, or alloys of alkali metals and alkaline earth metals.

  It is preferable that both the anode and the cathode have a low resistance. Generally, a metal material is used, but an organic compound or an inorganic compound may be used.

  Such a 1st electrode layer and a 2nd electrode layer can be formed using the formation method of a general electrode layer, for example, sputtering method, a vacuum evaporation method, etc. are mentioned.

D. Next, the manufacturing method of the anchor layer forming coating solution of the present invention will be described. The manufacturing method of the anchor layer forming coating solution of the present invention adjusts the anchor layer forming coating solution by ring-opening a part of the glycidyl group of the silane-modified epoxy resin represented by the following chemical formula (1). It is characterized by this.

Here, in the formula (1), R ^a ~R ^e represents a methyl group or an ethyl group, may be the same or different.

  In the present invention, for example, a silane-modified epoxy resin composition containing a silane-modified epoxy resin, an epoxy curing agent, a silane curing catalyst, and a solvent is reacted at a predetermined temperature and time, and a part of the glycidyl group of the silane-modified epoxy resin. A ring-opening reaction can be performed to obtain an anchor layer forming coating solution. The anchor layer-forming coating liquid thus obtained has better coating suitability for a specific polycarbonate-based resin substrate than the silane-modified epoxy resin composition before the reaction. Moreover, when the anchor layer of the barrier substrate described above is formed using the anchor layer forming coating solution of the present invention, the adhesion between the polycarbonate resin substrate and the deposited film may be good. it can.

  In the present invention, the glycidyl group is preferably ring-opened within a predetermined range by a ring-opening reaction of the glycidyl group of the silane-modified epoxy resin. Since the ratio of the ring opening of the glycidyl group is the same as that described in the above-mentioned section “A. Anchor layer forming coating solution”, the description thereof is omitted here.

  The silane-modified epoxy resin, the epoxy curing agent, the silane curing catalyst, the solvent, and the like are the same as those described in the above-mentioned section “A. Anchor layer forming coating solution”, and the reaction conditions are described above. Since it is the same as that described in the section of “A. Anchor layer forming coating solution 1. Anchor agent (2) Method for producing anchor agent”, description thereof is omitted here.

E. Next, a method for manufacturing a barrier substrate of the present invention will be described. The method for producing a barrier substrate of the present invention comprises forming a polycarbonate resin film by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group, and irradiating the polycarbonate resin film with ionizing radiation to form a polycarbonate resin. A polycarbonate resin base material forming step for forming a base material;
An anchor layer forming step of forming an anchor layer by applying and curing the anchor layer forming coating solution obtained by the above-described method for producing an anchor layer forming coating solution on the polycarbonate resin substrate;
And a vapor deposition film forming step of forming a vapor deposition film on the anchor layer.

  According to the present invention, by irradiating the polycarbonate resin film with ionizing radiation, a polycarbonate resin substrate having high heat resistance, improved dimensional stability and linear expansion coefficient can be obtained. Further, when the polycarbonate resin film is formed into a sheet, a conventional method can be used, and it is possible to easily produce a continuous sheet polycarbonate resin substrate.

  In the present invention, since the above-described anchor layer forming coating solution is used, the coating suitability to the polycarbonate-based resin base material having the above-described characteristics is good, and the deterioration of the barrier property due to coating unevenness is avoided. Can do. Moreover, since an anchor layer is formed by apply | coating this coating liquid for anchor layer formation, the polycarbonate-type resin base-material surface can be smoothed. For this reason, it becomes possible to form a dense vapor deposition film. Furthermore, by using the anchor layer forming coating solution, an anchor layer having high adhesion to the polycarbonate resin substrate and the deposited film can be obtained. Therefore, it is possible to obtain a barrier substrate having a good barrier property against oxygen and water vapor.

  The polycarbonate resin base material forming step and the vapor deposition film forming step are the same as those described in the respective sections of the polycarbonate resin base material and the vapor deposition film in “B. Barrier substrate” described above. The description in is omitted. Hereinafter, the anchor layer forming step will be described.

1. Anchor layer forming step In the anchor layer forming step of the present invention, the anchor layer forming coating solution obtained by the above-described method for producing an anchor layer forming coating solution is applied and cured on the polycarbonate resin substrate. This is a step of forming an anchor layer.

  The application method of the anchor layer forming coating solution is not particularly limited as long as it can be applied onto a polycarbonate resin substrate. For example, the bar coating method, the spin coating method, the blade coating method, the roll coating method, and the gravure coating method. , Spray coating method, casting method, dipping method, ink jet method, flexographic printing method and the like.

The temperature at which the anchor layer forming coating solution thus applied is cured is not particularly limited as long as it is a temperature at which the anchor layer forming coating solution can be completely cured. Although it varies depending on the types and contents of the epoxy resin, epoxy curing agent and silane curing catalyst, and the reaction time, it is usually about 80 ° C. to 180 ° C., preferably 100 ° C. to 160 ° C. Further, the heating time is not particularly limited as long as it is a time that can completely cure the anchor layer forming coating solution as described above. The silane-modified epoxy resin, the epoxy curing agent, and the silane curing catalyst are not particularly limited. Although it varies depending on the type and content and reaction temperature, it can be set in about 5 minutes to 2 hours, preferably in the range of 10 minutes to 1 hour.
The anchor layer can be formed by completely curing the anchor layer forming coating solution under such reaction conditions.

  The anchor layer forming coating solution is described in the above-mentioned sections “A. Anchor layer forming coating solution” and “D. Method for producing anchor layer forming coating solution”. Description is omitted.

2. Overcoat layer formation process In this invention, the overcoat layer formation process which forms an overcoat layer on a vapor deposition film may be performed. In this overcoat layer forming step, a polycarbonate resin base material on which an anchor layer and a vapor deposition film are formed, and a transfer body provided with a thermosetting resin film containing a polyfunctional epoxy resin on a support, the vapor deposition film And the thermosetting resin film are arranged so as to face each other, the transfer process of peeling the support of the transfer body and transferring the thermosetting resin film onto the vapor deposition film, and the transferred thermosetting resin It is preferable to have a curing step of thermally curing the film to form an overcoat layer.

  In such an overcoat layer forming step, a thermosetting resin containing a polyfunctional epoxy resin is very suitable as an overcoat layer for coating a vapor-deposited film, and is applied on a support. It is sometimes used that it becomes a coating film (thermosetting resin film) having appropriate adhesiveness that can be transferred to another surface to be transferred.

  According to the above-mentioned overcoat layer forming step, it is not a method of directly applying a thermosetting resin on a vapor deposition film, but a method of transferring a coating film (thermosetting resin film) on another support in advance. An overcoat layer can be formed by laminating the deposited film and curing it. Therefore, in the overcoat layer forming step, the vapor deposition film does not come into contact with the solvent contained in the thermosetting resin, and also does not come into contact with a member such as the head of the coating machine. Absent. Therefore, the barrier property can be improved as compared with the case where the thermosetting resin is directly applied onto the deposited film.

  Since the overcoat layer forming step is described in the above-mentioned section “B. Barrier substrate 4. Overcoat layer”, description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
The following anchor layer forming coating solution is applied onto a polycarbonate resin base material (Bayer's product, by hole DP1202 (Apec film), 200 μm thickness) made of a polycarbonate resin represented by the following chemical formula, and cured to anchor. A layer was formed.

(Preparation of anchor layer forming coating solution)
Silane-modified epoxy resin: 47% silica hybrid (Arakawa Chemical Co., Ltd., Composeran E) ... 100 parts by weight Epoxy curing agent: 100% by weight 4-methylhexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd.) ) Ricacid) ... 26 parts by weight-Silane curing catalyst: 100% by weight of tin octylate (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.)
... 0.9 parts by weight The above-mentioned silane-modified resin, epoxy curing agent and silane curing catalyst were mixed and reacted by stirring at 80 ° C for 30 minutes to obtain an anchor layer forming coating solution.

[Example 2]
In Example 1, an anchor layer was formed in the same manner as in Example 1 except that the reaction time was 10 minutes when preparing the anchor layer forming coating solution.

[Example 3]
In Example 1, an anchor layer was formed in the same manner as in Example 1 except that the reaction time was 1 hour when preparing the anchor layer forming coating solution.

[Comparative Example 1]
In Example 1, an anchor layer was formed in the same manner as in Example 1 except that the reaction was not performed when the anchor layer forming coating solution was prepared.

[Evaluation]
The coating state of the coating liquid for anchor layer formation in Examples 1 to 3 and Comparative Example 1 was observed. Table 1 shows the viscosity and coating suitability of the anchor layer forming coating solution, the ratio of ring opening of the glycidyl group of the silane-modified epoxy resin in the anchor layer forming coating solution, and the anchor layer on the polycarbonate resin substrate. 2 shows the oxygen gas permeability and water vapor permeability of the laminate in which is formed.
As for coating suitability, “○” indicates that the coating can be applied uniformly, interference fringes are observed due to unevenness in the film thickness, and “△” indicates that coating is not uniform even visually, and indicates that the coating is completely repelled. Indicated by “x”.
Further, the ratio of ring opening of the glycidyl group, oxygen gas permeability and water vapor permeability of the silane-modified epoxy resin were measured by the methods described above.

[Example 4]
A SiO _x film was formed by sputtering on the laminate obtained in Example 1, and FX-C310L202 (trade name) manufactured by Nippon Shokubai Co., Ltd. was used as an overcoat layer on the SiO _x film at a film thickness of 2 μm. Formed. Furthermore, a SiO _x film was formed on the overcoat layer by a sputtering method, and an overcoat layer similar to the above was formed on the SiO _x film to produce a barrier substrate for a flexible organic EL display.
The obtained barrier substrate had a water vapor transmission rate of 0.01 g / m ² / day or less and an oxygen gas transmission rate of 0.01 cc / m ² / day / atm or less, and exhibited good barrier properties.

It is a schematic sectional drawing which shows an example of the barrier property board | substrate of this invention. It is a schematic sectional drawing which shows the other example of the barrier property board | substrate of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Polycarbonate-type resin base material 2 ... Anchor layer 3 ... Deposition film 4 ... Overcoat layer

Claims (18)

The ratio of the ring opening of the glycidyl group of the anchor agent to the silane-modified epoxy resin, which includes an anchor agent obtained by polymerizing a silane-modified epoxy resin represented by the following chemical formula (1) and is measured by infrared spectroscopy, is 5 A coating solution for forming an anchor layer, characterized in that it is in the range of% to 60%.

(Here, in formula (1), R ^{a to} R ^e represent a methyl group or an ethyl group, and may be the same or different.)   The anchor layer forming coating solution according to claim 1, comprising an epoxy curing agent and a silane curing catalyst.   Viscosity is in the range of 5 mPa · s to 100 mPa · s at 25 ° C. The anchor layer-forming coating solution according to claim 1 or 2. A polycarbonate resin substrate obtained by irradiating a polycarbonate resin film obtained by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group with ionizing radiation, and an anchor layer formed on the polycarbonate resin substrate And a barrier substrate having a deposited film formed on the anchor layer,
The barrier layer is characterized in that the anchor layer is a cured product of a silane-modified epoxy resin represented by the following chemical formula (1).

(Here, in formula (1), R ^{a to} R ^e represent a methyl group or an ethyl group, and may be the same or different.)   5. The barrier substrate according to claim 4, wherein the anchor layer has a linear expansion coefficient of 100 ppm / ° C. or less at 50 ° C. to 150 ° C. 5.   The barrier substrate according to claim 4 or 5, wherein the total light transmittance of the anchor layer is 80% or more. The barrier substrate according to any one of claims 4 to 6, wherein the bisphenol compound is represented by the following chemical formula (2).

(In the formula (2), R ¹ and R ² are independently of each other hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and an aryl having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms, X is carbon, m is 4 or 5, R ³ and R ⁴ are independently selected for each X, and are independently hydrogen or An alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ simultaneously represent an alkyl group on at least one X atom.) The barrier substrate according to any one of claims 4 to 6, wherein the bisphenol compound is represented by the following chemical formula (3).

(Here, in formula (3), R ^{5 to} R ⁸ are hydrogen, or an alkyl group, aralkyl group or alkoxy group having 1 to 7 carbon atoms, and each of R ^{5 to} R ⁸ may be the same or different. .)   The barrier substrate according to any one of claims 4 to 8, a first electrode layer formed on the barrier substrate, at least a light emitting layer formed on the first electrode layer. An organic electroluminescent layer, and a second electrode layer formed on the organic electroluminescent layer. A method for producing a coating liquid for forming an anchor layer, comprising adjusting a coating liquid for forming an anchor layer by subjecting a part of a glycidyl group of a silane-modified epoxy resin represented by the following chemical formula (1) to a ring-opening reaction. .

(Here, in formula (1), R ^{a to} R ^e represent a methyl group or an ethyl group, and may be the same or different.)   The method for producing a coating liquid for anchor layer formation according to claim 10, wherein the glycidyl group of the silane-modified epoxy resin is ring-opened within a range of 5% to 60% by the ring-opening reaction.   The method for producing an anchor layer forming coating solution according to claim 10 or 11, wherein an epoxy curing agent and a silane curing catalyst are used in the ring-opening reaction. Polycarbonate resin base material formation in which a polycarbonate resin film is formed by polymerizing a bisphenol compound containing an aliphatic cyclic hydrocarbon group, and the polycarbonate resin base material is formed by irradiating the polycarbonate resin film with ionizing radiation Process,
On the said polycarbonate-type resin base material, the coating liquid for anchor layer formation obtained by the manufacturing method of the coating liquid for anchor layer formation of any one of Claim 10 to 12 is applied. An anchor layer forming step of forming an anchor layer by curing;
And a vapor deposition film forming step of forming a vapor deposition film on the anchor layer. The method for producing a barrier substrate according to claim 13, wherein the bisphenol compound is represented by the following chemical formula (2).

(In the formula (2), R ¹ and R ² are independently of each other hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and an aryl having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms, X is carbon, m is 4 or 5, R ³ and R ⁴ are independently selected for each X, and are independently hydrogen or An alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ simultaneously represent an alkyl group on at least one X atom.) The method for producing a barrier substrate according to claim 13, wherein the bisphenol compound is represented by the following chemical formula (3).

(Here, in formula (3), R ^{5 to} R ⁸ are hydrogen, or an alkyl group, aralkyl group or alkoxy group having 1 to 7 carbon atoms, and each of R ^{5 to} R ⁸ may be the same or different. .)   The barrier substrate according to any one of claims 13 to 15, wherein the ionizing radiation is irradiated in a deoxygenated atmosphere in the polycarbonate-based resin base material forming step. Method.   The method for producing a barrier substrate according to claim 16, wherein in the polycarbonate-based resin base material forming step, the ionizing radiation is irradiated under heating. 18. The heating according to claim 13, wherein heating in a deoxygenated atmosphere is performed after the irradiation with the ionizing radiation in the polycarbonate-based resin base material forming step. Manufacturing method of barrier substrate.

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