JPWO2013147189A1 - Curable resin composition for vapor deposition, resin protective film, organic optical device, and manufacturing method of organic optical device - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition for vapor deposition that can be deposited on a substrate at a low temperature and with a high vapor deposition efficiency, and that can form a vapor deposited film having excellent adhesion to an inorganic material film. And Moreover, an object of this invention is to provide the manufacturing method of the resin protective film manufactured using this curable resin composition for vapor deposition, an organic optical device, and an organic optical device. The present invention relates to a curable resin composition for vapor deposition that forms a vapor deposition film on a substrate by volatilization by heating in an atmospheric pressure or a reduced pressure atmosphere, and a polythiol having two or more thiol groups in one molecule A compound, a polyene compound having two or more carbon-carbon double bonds in one molecule, and a photopolymerization initiator, wherein the polythiol compound and the polyene compound have a molecular weight of 230 to 500 It is a curable resin composition.

Description

The present invention relates to a curable resin composition for vapor deposition that can be deposited on a substrate at a low temperature and with high vapor deposition efficiency and can form a vapor deposited film having excellent adhesion to an inorganic material film. Moreover, this invention relates to the manufacturing method of the resin protective film manufactured using this curable resin composition for vapor deposition, an organic optical device, and an organic optical device.

In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence elements and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.

The organic electroluminescence element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. The organic electroluminescence element has an advantage that it is more visible than a liquid crystal display element that requires a backlight, can be made thinner, and can be driven by a DC low voltage. It is attracting attention as a next-generation display.

Organic thin-film solar cell elements are superior to solar cells using inorganic semiconductors in terms of cost, large area, ease of manufacturing processes, and the like, and various configurations have been proposed. Specifically, for example, Non-Patent Document 1 discloses an organic solar cell element using a laminated film of phthalocyanine copper and a perylene dye.

These organic thin film elements have a problem that when the organic layer and the electrode are exposed to the outside air, the performance is rapidly deteriorated. Therefore, in order to improve stability and durability, it is indispensable to seal the organic thin film element and shield it from moisture and oxygen in the atmosphere.
As a method of sealing the organic thin film element, a method of sealing with a metal can provided with a water absorbing agent inside is generally used. However, in the method of sealing with a metal can, it is difficult to reduce the thickness of the organic optical device. Therefore, development of a method for sealing an organic thin film element that does not use a metal can has been promoted.

Patent Document 1 discloses a method of sealing an organic layer and an electrode of an organic thin film element with a laminated film of a resin film formed by a CVD method and a silicon nitride (SiN _x ) film. Here, the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.

In the method of sealing with a silicon nitride film disclosed in Patent Document 1, the organic thin film element is formed when the silicon nitride film is formed due to unevenness on the surface of the organic thin film element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. May not be completely covered with a film. If the coating with the silicon nitride film is incomplete, moisture will enter the organic layer through the silicon nitride film.
As a method for preventing moisture from entering the organic layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film, and Patent Document 3 discloses an inorganic material film. A method of forming a resin film by applying a liquid acrylic resin on the substrate is disclosed.

However, in the method disclosed in Patent Document 2, sufficient effects can be obtained if the thickness of the inorganic material film is not increased in order to completely cover the surface of the organic thin film element even when there are large unevenness or adhesion of foreign matter. For this reason, there is a problem that the internal stress due to the silicon nitride film is increased or the productivity is deteriorated. In addition, the method disclosed in Patent Document 3 has problems such as insufficient adhesion between the inorganic material film and the resin film, and internal stress due to curing shrinkage of the resin film.

In addition, organic thin film elements such as organic electroluminescence elements and organic thin film solar cell elements have been studied for flexibility, and can be applied to a roll-to-roll system in addition to being able to cope with curved surfaces. Therefore, it is advantageous in terms of cost. However, the plastic film substrate used for making the organic thin film element flexible has a problem that it is inferior in water vapor barrier property as compared with the glass substrate. Therefore, when using a plastic film as a base material, various gases such as water vapor and oxygen are blocked by forming a metal oxide layer such as aluminum oxide, magnesium oxide, and silicon oxide on the surface to provide barrier properties. It is necessary to do.

Even when a metal oxide layer such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic film, the coating may be incomplete due to surface irregularities, adhesion of foreign matter, generation of cracks due to internal stress, etc. As disclosed in Patent Document 4, it is necessary to stack a metal oxide film through an organic film.

JP 2000-223264 A JP 2005-522891 A JP 2001-307873 A JP 2008-149710 A

Applied Physics Letters (1986, Vol. 48, P. 183)

An object of the present invention is to provide a curable resin composition for vapor deposition that can be deposited on a substrate at a low temperature and with a high vapor deposition efficiency, and that can form a vapor deposited film having excellent adhesion to an inorganic material film. And Moreover, an object of this invention is to provide the manufacturing method of the resin protective film manufactured using this curable resin composition for vapor deposition, an organic optical device, and an organic optical device.

The present invention relates to a curable resin composition for vapor deposition that forms a vapor deposition film on a substrate by volatilization by heating in an atmospheric pressure or a reduced pressure atmosphere, and a polythiol having two or more thiol groups in one molecule A compound, a polyene compound having two or more carbon-carbon double bonds in one molecule, and a photopolymerization initiator, wherein the polythiol compound and the polyene compound have a molecular weight of 230 to 500 It is a curable resin composition.
The present invention is described in detail below.

Conventionally, a curable resin composition containing an acrylic resin and a photo-radical polymerization initiator has been used for a resin film deposited and cured on a base material such as an inorganic material film or a resin substrate formed on an organic thin film element. However, such a curable resin composition has to be heated at a high temperature in order to vaporize the acrylic resin and the radical photopolymerization initiator. In addition, the obtained resin film has a problem that the adhesion to the inorganic material film is not sufficient.
By using a polyene-polythiol-based photocurable resin instead of an acrylic resin, the present inventors can perform vapor deposition at a low temperature, and can form a vapor deposition film having excellent adhesion with an inorganic material film. It has been found that a curable resin composition can be obtained. Furthermore, the present inventors have found that the deposition efficiency can be increased by setting the molecular weights of the polythiol compound and the polyene compound within a specific range, and the present invention has been completed. Such a curable resin composition for vapor deposition has a high vapor deposition efficiency, and the vapor deposition efficiency of the polythiol compound and the polyene compound is almost the same. Therefore, there is little residual unreacted monomer, and the vapor deposition film has uniform physical properties. Can be formed efficiently.

The curable resin composition for vapor deposition of the present invention contains a polythiol compound having two or more thiol groups in one molecule and a polyene compound having two or more carbon-carbon double bonds in one molecule. . By using such a polyene-polythiol-based photocurable resin, the vapor deposition film obtained by vapor deposition and curing of the curable resin composition for vapor deposition of the present invention has excellent adhesion to the inorganic material film, And generation | occurrence | production of the crack by the internal stress by hardening shrinkage | contraction of this vapor deposition film can be suppressed.

The polythiol compound having two or more thiol groups in one molecule and the polyene compound having two or more carbon-carbon double bonds in one molecule have a molecular weight lower limit of 230 and an upper limit of 500. . By setting the molecular weight within such a range, the curable resin composition for vapor deposition of the present invention has high vapor deposition efficiency, and the vapor deposition efficiency of the polythiol compound and the polyene compound is approximately the same. Therefore, it is possible to efficiently form a vapor-deposited film having uniform physical properties.
In this specification, a polythiol compound having two or more thiol groups in one molecule and having a molecular weight of 230 to 500 is also simply referred to as a polythiol compound, and two or more carbon-carbon doubles in one molecule. A polyene compound having a bond and a molecular weight of 230 to 500 is also simply referred to as a polyene compound.

When the molecular weight is less than 230, the polythiol compound and / or the polyene compound is likely to be volatilized, causing a problem such as being sucked into a vacuum pump, and the deposition efficiency is lowered. When the molecular weight exceeds 500, the polythiol compound and / or the polyene compound are less likely to volatilize, and the deposition efficiency decreases. Moreover, when the molecular weight of only one of the polythiol compound or the polyene compound is less than 230 or exceeds 500, the difference in vapor deposition efficiency between the polythiol compound and the polyene compound increases, and the unreacted monomer tends to remain.
The preferable lower limit of the molecular weight of the polythiol compound is 234, the preferable upper limit is 488, the more preferable lower limit is 300, and the more preferable upper limit is 450. Moreover, the preferable minimum of the molecular weight of the said polyene compound is 246, a preferable upper limit is 450, a more preferable minimum is 300, and a more preferable upper limit is 423.

The molecular weight ratio between the polythiol compound and the polyene compound is preferably 1: 0.5 to 1: 1.8. When the molecular weight ratio is out of the above range, the difference in vapor deposition efficiency between the polythiol compound and the polyene compound increases, and the unreacted monomer may easily remain. The molecular weight ratio between the polythiol compound and the polyene compound is more preferably 1: 0.6 to 1: 1.5, and still more preferably 1: 0.7 to 1: 1.3.

The polythiol compound and the polyene compound have a weight loss rate of 10% or less at 150 ° C. determined by simultaneous differential thermothermal gravimetric measurement (TG-DTA measurement) at a heating rate of 10 ° C./min in an atmospheric pressure nitrogen atmosphere. It is preferably 25% or more at 300 ° C. By setting the weight reduction rate within such a range, the curable resin composition for vapor deposition of the present invention has a high vapor deposition efficiency, and the vapor deposition efficiency of the polythiol compound and the polyene compound is approximately the same. It is possible to efficiently form a vapor deposition film having uniform physical properties with little residual reaction monomer.
The simultaneous differential thermothermal weight measurement can be performed using, for example, a TG / DTA apparatus (for example, “EXSTAR TG / DTA7000” manufactured by Seiko Instruments Inc.).

When the weight reduction rate exceeds 10% at 150 ° C., the polythiol compound and / or the polyene compound is likely to volatilize, causing a problem such as being sucked into the vacuum pump, and the deposition efficiency may be lowered. In addition, when the weight reduction rate of only one of the polythiol compound and the polyene compound exceeds 10% at 150 ° C., the difference in deposition efficiency between the polythiol compound and the polyene compound increases, and the unreacted monomer tends to remain. . The more preferable upper limit of the weight reduction rate of the polythiol compound at 150 ° C. is 8%, and the more preferable upper limit is 5%. The more preferable upper limit of the weight reduction rate of the polyene compound at 150 ° C. is 8%, the still more preferable upper limit is 7%, and the particularly preferable upper limit is 5%.
The lower limit of the weight reduction rate at 150 ° C. is not particularly limited, and may be 0%.

When the weight reduction rate is less than 25% at 300 ° C., the polythiol compound and / or the polyene compound are less likely to volatilize, and the deposition efficiency may decrease. In addition, when the weight reduction rate of only one of the polythiol compound and the polyene compound is less than 25% at 300 ° C., the difference in deposition efficiency between the polythiol compound and the polyene compound increases, and the unreacted monomer tends to remain. . A more preferable lower limit of the weight reduction rate of the polythiol compound at 300 ° C. is 55%, and a further preferable lower limit is 70%. Further, the more preferable lower limit of the weight reduction rate of the polyene compound at 300 ° C. is 35%, and the more preferable lower limit is 70%.
The upper limit of the weight reduction rate at 300 ° C. is not particularly limited, and may be 100%.

As the polythiol compound, an ester obtained by a reaction between a mercaptocarboxylic acid and a polyhydric alcohol is preferably used.
Examples of the ester obtained by the reaction of the mercaptocarboxylic acid and the polyhydric alcohol include pentaerythritol tetrakis (3-mercaptobutyrate) (molecular weight 488, for example, “PEMP” manufactured by SC Organic Chemical Co., Ltd.), tri Methylolpropane tris (3-mercaptopropionate) (molecular weight 356, for example, SC Organic Chemicals, "TMMP"), trimethylolpropane tris (3-mercaptobutyrate) (molecular weight 440, for example, manufactured by Showa Denko KK "TPMB"), methylol ethane tris (3-mercaptobutyrate) (molecular weight 428, for example, Showa Denko KK), trimethylol ethane tris (3-mercaptopropionate) (molecular weight 342), 1,4-bis ( 3-mercaptobutyryloxy) butane (molecular weight 294, For example, “Karenz MT BD1” manufactured by Showa Denko KK, butanediol bisthioglycolate (molecular weight 239, for example, “BDTG” manufactured by Sakai Chemical Co., Ltd.), hexanediol bisthioglycolate (molecular weight 286, for example, Sakai Chemical) And “HDTG”). Among these, trimethylolpropane tris (3-mercaptopropionate) is preferable because of high vapor deposition efficiency and high curability. Examples of other polythiol compounds include 1,10-dodecanedithiol (molecular weight 234, for example, manufactured by Wako Pure Chemical Industries, Ltd.).
These polythiol compounds may be used independently and 2 or more types may be used together.

As the polyene compound, a polyene compound having an aromatic ring is preferably used. By using a polyene compound having an aromatic ring, the resin protective film obtained by curing the curable resin composition of the present invention has excellent heat resistance. More specifically, the glass transition point is raised, and the resin protective film is highly reliable at high temperatures.
Examples of the polyene compound having an aromatic ring include diallyl phthalate (molecular weight 246), diallyl isophthalate (molecular weight 246), triallyl 1,3,5-benzenetricarboxylate (molecular weight 330), diallyl diphenate (molecular weight 322, For example, “DAD” manufactured by Nippon Distillation Industries Co., Ltd., diallyl 2,3-naphthalenecarboxylate (molecular weight 296, for example, “DANO” manufactured by Nippon Distillation Co., Ltd.), diphenyl diallylsilane (molecular weight 261, for example, Tokyo Chemical Industry Co., Ltd.) 2,2′-diallylbisphenol A (molecular weight 308, for example, “DABPA” manufactured by Daiwa Kasei Co., Ltd.), pyromellitic acid tetraallyl (molecular weight 414, for example, manufactured by Wako Pure Chemical Industries, Ltd.), and the like. Of these, diallyl 2,3-naphthalenecarboxylate is preferred because of its low viscosity and high vapor deposition efficiency. These polyene compounds having an aromatic ring may be used alone or in combination of two or more.

Further, as the polyene compound, a polyene compound having no aromatic ring can also be used. Examples of the polyene compound having no aromatic ring include triallyl isocyanurate (molecular weight 249, for example, “TAIC” manufactured by Nippon Kasei Co., Ltd.), trimethallyl isocyanurate (molecular weight 291; for example, manufactured by Nippon Kasei Co., Ltd., “ TMAIC "), pentaerythritol triallyl ether (molecular weight 242; for example," T-30P "manufactured by Daiso Corporation). Of these, triallyl isocyanurate is preferred because of its low viscosity and high curability. These polyene compounds having no aromatic ring may be used alone or in combination of two or more.

As the polyene compound, a compound having a (meth) acryloyl group is also preferably used.
Examples of the compound having the (meth) acryloyl group include 1,9-nonanediol diacrylate (molecular weight 268, for example, “Light acrylate 1,9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.), 1,12-dodecanediol. Dimethacrylate (molecular weight 340, for example, “CD262” manufactured by Sartomer, Inc.), dimethylol-tricyclodecanediacrylate (molecular weight 304, for example, “Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.), neopentyl glycol hydroxypivalate Acrylic acid adduct (molecular weight 291; for example, “Light acrylate HPP-A” manufactured by Kyoeisha Chemical Co., Ltd.), trimethylolpropane triacrylate having two or more (meth) acryloyl groups (for example, “Light acrylate manufactured by Kyoeisha Chemical Co., Ltd.) TMP-A "(Molecular 296)), isocyanuric acid triacrylate (molecular weight 423, for example, manufactured by Toagosei Co., Ltd., "Aronix M-315"), and the like. These compounds having a (meth) acryloyl group may be used alone or in combination of two or more.
In the present specification, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, and the “(meth) acrylate” means an acrylate or a methacrylate.

Furthermore, as said polyene compound, vinyl ether compounds, such as cyclohexane dimethanol divinyl ether, allyl ether compounds, such as pentaerythritol triallyl ether, vinyl compounds, such as styrene and divinylbenzene, etc. are used suitably.

When the polyene compound contains a polyene compound having no aromatic ring, the content ratio of the polyene compound having no aromatic ring is the heat resistance of the resin protective film obtained by curing the curable resin composition. From the viewpoint, the preferable upper limit is 50% by weight with respect to the whole polyene compound.

The blending ratio of the polythiol compound and the polyene compound in the curable resin composition for vapor deposition of the present invention is not particularly limited, but blended so that the polythiol compound: the polyene compound = 25: 75 to 68:32 by weight ratio. It is preferable to do.
Further, the molar ratio between the thiol group of the polythiol compound and the carbon-carbon double bond of the polyene compound is thiol group: carbon-carbon double bond = 1: 0.4 to 1: 2.5. It is preferable to do. When the number of moles of thiol group exceeds 2.5 times the number of moles of carbon-carbon double bonds, or when the number of moles of thiol group is less than 0.4 times the number of moles of carbon-carbon double bonds Unreacted monomers are likely to remain, and outgassing may occur or a vapor deposition film having uniform physical properties may not be obtained efficiently. The polythiol compound and the polyene compound are more preferably blended so that thiol group: carbon-carbon double bond = 1: 0.5 to 1: 2, and blended so as to be close to 1: 1. More preferably.

The curable resin composition for vapor deposition of the present invention may contain other curable compounds in addition to the polythiol compound and the polyene compound as long as the object of the present invention is not impaired.
Examples of the other curable compounds include epoxy resins, oxetane resins, and episulfide resins.

The content of the other curable compounds is the viscosity of the curable resin composition for vapor deposition, the heat resistance of the vapor-deposited film obtained by vapor-depositing and curing the obtained curable resin composition for vapor deposition, and adhesion to the inorganic material film. From the viewpoint of suppressing the curing shrinkage of the deposited film, the preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the total of the polythiol compound and the polyene compound. The upper limit with more preferable content of the said other sclerosing | hardenable compound is 30 weight part.

The curable resin composition for vapor deposition of the present invention contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzophenone photopolymerization initiators such as benzophenone, p-aminobenzophenone, p, p′-dimethylaminobenzophenone, methyl orthobenzoylbenzoate and 4-benzoyl-4′-methyldiphenyl sulfide. Acetophenone, benzaldehyde, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, oligo Acetophenone photopolymerization initiators such as [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone], 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin Propyl Benzoin ether photopolymerization initiators such as ether and benzoin isobutyl ether, azo compounds such as 2,2′-azobisisobutyronitrile, diazo compounds such as diazoaminobenzene, 4,4′-di Azidostilbene-p-phenylenebisazide, isopropylthioxanthone, diethylthioxanthone, acylphosphine oxide, diphenylethanedione, camphorquinone, anthraquinone, Michler's ketone and the like. These photoinitiators may be used independently and 2 or more types may be used together.

In the curable resin composition for vapor deposition of the present invention, the content of the photopolymerization initiator is selected from the viewpoint of the polymerization rate of the obtained curable resin composition for vapor deposition, the curing reaction rate, and the uniformity of the cured product. A preferable lower limit is 0.0001 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total of the compound and the polyene compound. The minimum with more preferable content of the said photoinitiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.

The curable resin composition for vapor deposition of the present invention may contain a photosensitizer. The photosensitizer has a role of further improving the polymerization initiation efficiency of the photopolymerization initiator and further promoting the curing reaction of the curable resin composition for vapor deposition of the present invention.

Examples of the photosensitizer include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o -Methyl benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'methyldiphenyl sulfide and the like. These photosensitizers may be used independently and 2 or more types may be used together.

The content of the photosensitizer is based on a total of 100 parts by weight of the polythiol compound and the polyene compound from the viewpoint of the sensitization effect and the light transmittance to the deep part of the curable resin composition for vapor deposition. The preferred lower limit is 0.03 parts by weight, and the preferred upper limit is 2 parts by weight. The minimum with more preferable content of the said photosensitizer is 0.05 weight part, and a more preferable upper limit is 1 weight part.

The curable resin composition for vapor deposition of the present invention may contain a polymerization inhibitor.
Examples of the polymerization inhibitor include N-nitrosoarylhydroxylamine salts, phenol derivatives, hydroquinone derivatives, and the like.
Examples of the N-nitrosoarylhydroxylamine salt include ammonium salt, sodium salt, potassium salt, magnesium salt, strontium salt, aluminum salt, copper salt, zinc salt, cerium salt and iron salt of N-nitrosophenyl hydroxylamine. , Nickel salt, cobalt salt and the like. Of these, an ammonium salt of N-nitrosophenyl hydroxylamine is preferable.
Examples of the phenol derivative include p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,2-methylene-bis (4-methyl-6-t-butylphenol) and the like. . Of these, 2,2-methylene-bis (4-methyl-6-tert-butylphenol) is preferable.
Examples of the hydroquinone derivative include hydroquinone and hydroquinone monomethyl ether. Especially, even if it adds to a curable resin composition for vapor deposition in large quantities, since it is hard to volatilize at the time of vapor deposition and it is hard to transfer to a vapor deposition film, N-nitrosoarylhydroxylamine salt is preferable at the point which does not inhibit photocuring.
These polymerization inhibitors may be used independently and 2 or more types may be used together.

The content of the polymerization inhibitor is preferably 0.0001 parts by weight with respect to a total of 100 parts by weight of the polythiol compound and the polyene compound from the viewpoint of curability of the resulting curable resin composition for vapor deposition. The preferred upper limit is 1.0 part by weight. The minimum with more preferable content of the said polymerization inhibitor is 0.0005 weight part, and a more preferable upper limit is 0.1 weight part.

The curable resin composition for vapor deposition of the present invention may contain an adhesion promoter.
Examples of the adhesion-imparting agent include silane coupling agents such as glycidoxytrimethoxysilane, glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, Examples include titanium coupling agents and aluminum coupling agents. These adhesiveness imparting agents may be used alone or in combination of two or more.

The curable resin composition for vapor deposition according to the present invention further includes an antioxidant, a filler, a curing accelerator, a plasticizer, a surfactant, a heat stabilizer, a flame retardant, and the like within a range not impairing the object of the present invention. You may contain additives, such as an antistatic agent, an antifoamer, a leveling agent, a ultraviolet absorber, and an organic solvent, as needed.

The preferable upper limit of the viscosity of the curable resin composition for vapor deposition according to the present invention measured using an E-type viscometer under the conditions of 25 ° C. and 2.5 rpm is 500 mPa · s. When the said viscosity exceeds 500 mPa * s, in order to vapor-deposit the curable resin composition for vapor deposition obtained, it may be necessary to heat at high temperature. The upper limit with a more preferable viscosity of the curable resin composition for vapor deposition of this invention is 450 mPa * s, and a more preferable upper limit is 200 mPa * s.
Moreover, although it is preferable that the curable resin composition for vapor deposition of this invention is low viscosity, a substantial minimum is 15 mPa * s.

The method for preparing the curable resin composition for vapor deposition of the present invention is not particularly limited. For example, the polythiol compound, the polyene compound, the photopolymerization initiator, and various photosensitizers added as necessary. Additives can be used alone or in combination with various known kneaders such as planetary stirrers, homodispers, universal mixers, Banbury mixers, kneaders, two rolls, three rolls, extruders, etc. at room temperature or under heating. Examples thereof include a method of uniformly kneading under conditions such as normal pressure, reduced pressure, increased pressure, or an inert gas stream.

The resin protective film obtained by photocuring the curable resin composition for vapor deposition of the present invention is also one aspect of the present invention.

Examples of the method of photocuring the curable resin composition for vapor deposition of the present invention include a method of irradiating light with a wavelength of 300 nm to 400 nm and an integrated light amount of 300 to 3000 mJ / cm ² .

The light source for irradiating light to the curable resin composition for vapor deposition of the present invention is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, Examples include a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used independently and 2 or more types may be used together.
These light sources are appropriately selected according to the absorption wavelength of the photopolymerization initiator.

Examples of the light irradiation means to the curable resin composition for vapor deposition of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. The irradiation means may be used.

An organic optical device in which an organic thin film element is protected by a resin protective film obtained by vapor deposition and photocuring the curable resin composition for vapor deposition of the present invention is also one aspect of the present invention. By protecting the organic thin film element with a resin protective film obtained by vapor-depositing and photocuring the curable resin composition for vapor deposition of the present invention, it is possible to sufficiently prevent moisture from entering the organic thin film element. The performance and durability of the element can be maintained high, and the organic optical device can be thinned.
Also, a step of depositing the curable resin composition for vapor deposition of the present invention on the organic thin film element, and a step of photocuring the deposited curable resin composition for vapor deposition to form a resin protective film on the organic thin film element A method for producing an organic optical device having the above is also one aspect of the present invention.

The said organic thin film element is not specifically limited, For example, an organic electroluminescent element (henceforth "organic EL element"), an organic thin film solar cell element, etc. are mentioned.
The organic EL element is formed, for example, by vacuum-depositing a hole injection electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an electron injection electrode in order on a substrate. Can do.

When the organic thin film element is an organic EL element, the organic optical device may have a bottom emission structure in which light is extracted from the lower surface side (side where the element is not formed on the substrate), or the upper surface side (element is formed on the substrate). It may be a top emission structure in which light is taken out from the side to be provided.

The organic thin film element is disposed on a substrate and covers a region including the organic thin film element before being protected by a resin protective film obtained by vapor deposition and photocuring the curable resin composition for vapor deposition of the present invention. As described above, it is preferably coated with an inorganic material film in advance.
The substrate is not particularly limited. For example, in a simple matrix type (passive type) optical device, a transparent glass substrate can be used. In an active matrix type optical device, a plurality of TFTs (thin film transistors) are formed on the transparent glass substrate. In addition, a TFT substrate provided with a planarization layer can be used.

Examples of the inorganic material constituting the inorganic material film include silicon nitride (SiN _x ), silicon oxide (SiO _x ), and aluminum oxide (Al ₂ O ₃ ). The inorganic material film may be a single layer or may be a laminate of a plurality of types of layers.

A method for coating the organic thin film element with the inorganic material film is not particularly limited. When the inorganic material film is made of silicon nitride or silicon oxide, a sputtering method, an electron cyclotron resonance (ECR) plasma CVD method, or the like can be given. It is done.
The sputtering method is preferably carried out under conditions of room temperature, power of 50 to 1000 W, and pressure of 0.001 to 0.1 Torr using, for example, argon gas or nitrogen gas alone or as a mixed gas as a carrier gas.
The ECR plasma CVD method uses, for example, a mixed gas of SiH ₄ and O ₂ (in the case of silicon oxide) or a mixed gas of SiH ₄ and N ₂ (in the case of silicon nitride), at a temperature of 30 ° C. to 100 ° C., It is preferable to carry out under the conditions of a pressure of 10 mTorr to 1 Torr, a frequency of 2.45 GHZ, and a power of 10 to 1000 W.

As a method for depositing the curable resin composition for vapor deposition of the present invention on the organic thin film element, it is preferable to use a flash vapor deposition method.

The step of depositing the curable resin composition for vapor deposition of the present invention on the organic thin film element can be performed at a low temperature.
Specifically, the preferable lower limit of the heating temperature when the curable resin composition for vapor deposition of the present invention is deposited on the organic thin film element is 150 ° C., and the preferable upper limit is 300 ° C. When the heating temperature is less than 150 ° C., the curable resin composition for vapor deposition of the present invention may not be sufficiently deposited on the organic thin film element. When the said heating temperature exceeds 300 degreeC, the curable resin composition for vapor deposition may harden | cure. A more preferable lower limit of the heating temperature is 170 ° C., and a more preferable upper limit is 250 ° C.

The step of depositing the curable resin composition for vapor deposition of the present invention on the organic thin film element is performed under atmospheric pressure or a reduced pressure atmosphere.
Specifically, the lower limit of the atmospheric pressure when the curable resin composition for vapor deposition of the present invention is vapor-deposited on the organic thin film element is 10 ⁻³ Pa, preferably the upper limit from the viewpoints of vapor deposition properties and decompression process time Is 100 Pa. A more preferable lower limit of the atmospheric pressure is 10 ⁻¹ Pa, and a more preferable upper limit is 50 Pa.

In the step of forming a resin protective film on the organic thin film element, the curable resin composition for vapor deposition of the present invention can be formed as the resin protective film of the present invention by being photocured by the method described above.

The thickness of the resin protective film formed on the organic optical device of the present invention is not particularly limited, but the effect of preventing the organic thin film element and the electrode from being pressed by the internal stress of the inorganic material film, and the thinning of the organic optical device From the viewpoint, the preferable lower limit is 0.1 μm, and the preferable upper limit is 20 μm. The more preferable lower limit of the thickness of the resin protective film is 0.3 μm, and the more preferable upper limit is 2 μm.

In the organic optical device of the present invention, it is preferable to further laminate an inorganic material film on the resin protective film in order to enhance the effect of protecting the organic thin film element from moisture and oxygen in the atmosphere. The inorganic material constituting the inorganic material film laminated on the resin protective film and the forming method are the same as the inorganic material film covering the organic thin film element described above.

Although the thickness of the inorganic material film formed on the resin protective film is not particularly limited, the preferable lower limit is 0.05 μm, preferably from the viewpoint of preventing moisture intrusion, preventing cracking of the inorganic material film, and forming time. The upper limit is 20 μm. The more preferable lower limit of the thickness of the inorganic material film formed on the resin protective film is 0.1 μm, and the more preferable upper limit is 10 μm.

In order to more strictly protect the organic optical device of the present invention from light and oxygen, two or more resin protective films and inorganic material films may be alternately laminated. The materials and forming methods of the resin protective film and the inorganic material film that are alternately stacked are the same as those of the resin protective film and the inorganic material film described above.

According to the present invention, there is provided a curable resin composition for vapor deposition that can be deposited on a substrate at a low temperature and with a high vapor deposition efficiency and can form a vapor deposition film having excellent adhesion to an inorganic material film. Can do. Moreover, according to this invention, the manufacturing method of the resin protective film manufactured using this curable resin composition for vapor deposition, an organic optical device, and an organic optical device can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Examples 1-21, Comparative Examples 1-15)
(1) Fabrication of a substrate on which an organic EL element is disposed A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode is formed to a thickness of 1000 mm is used as a substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd., The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible in other different ways. 200 mg of tris (8-hydroxyquinola) aluminum (Alq ₃ ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq ₃ was heated to form a light emitting layer having a thickness of 600 Å at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the light emitting layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to the tungsten resistance heating boat in the vacuum vapor deposition apparatus, and the aluminum wire 1 is applied to another tungsten boat. 0.0 g was added. Then, after reducing the pressure in the vapor deposition unit of the vacuum vapor deposition apparatus to 2 × 10 ⁻⁴ Pa and depositing 5 μm of lithium fluoride at a deposition rate of 0.2 kg / s, deposit 1000 μm of aluminum at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the 10 mm × 10 mm organic EL elements were arranged was taken out.

(2) Coating with inorganic material film A A mask having an opening of 13 mm × 13 mm is installed on the substrate on which the obtained organic EL element is arranged so as to cover the entire organic EL element, and plasma CVD is used. Thus, an inorganic material film A was formed.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0. The test was performed at 9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.

(3) Formation of Resin Protective Film According to the composition shown in Tables 1 to 5, each material was heated to 60 ° C. using a separable flask and uniformly stirred and mixed to prepare a curable resin composition for vapor deposition. .
A substrate on which an organic EL element coated with an inorganic material film A is placed is placed in a vacuum device, and 1 g of the curable resin composition for vapor deposition is placed in a heating boat installed in the vacuum device, and the pressure is reduced to 10 Pa. Then, the obtained curable resin composition for vapor deposition was heated at 200 ° C. on a 11 mm × 11 mm square portion including the organic EL element, and vacuum vapor deposition was performed so that the thickness became 1 μm. Thereafter, ultraviolet rays with a wavelength of 365 nm were irradiated in a vacuum environment using a high-pressure mercury lamp so that the irradiation amount was 3000 mJ / cm ^2, and the curable resin composition for vapor deposition was cured to form a resin protective film.
In addition, using a differential thermothermogravimetric simultaneous measurement device (“EXSTAR TG / DTA7000” manufactured by Seiko Instruments Inc.), differential polythermogravimetric and polyene compounds were subjected to simultaneous differential thermothermogravimetric measurement, and the temperature was increased in an atmospheric pressure nitrogen atmosphere. The weight loss rate at a temperature rate of 10 ° C./min, 150 ° C. and 300 ° C. was determined.
The results are shown in Tables 1-5.

(4) A mask having an opening of 12 mm × 12 mm is installed so as to cover the entire 11 mm × 11 mm resin protective film of the substrate on which the organic EL element on which the coating resin protective film is formed by the inorganic material film B is disposed. And the inorganic material film | membrane B was formed by plasma CVD method, and the organic optical device (organic EL element device) was obtained.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film B had a thickness of about 1 μm.

(Evaluation)
About the curable resin composition for vapor deposition and organic optical device which were obtained by the Example and the comparative example, it evaluated by the following method. The results are shown in Tables 1-5.

(1) Viscosity About the sealing agent for organic EL display elements obtained in each Example and each Comparative Example, using an E-type viscometer (manufactured by BROOKFIELD, “DV-III”), 25 ° C., 2.5 rpm The viscosity was measured under the following conditions.

(2) Deposition amount About 0.5 g of the curable resin composition for vapor deposition obtained in each example and each comparative example was placed in a heating boat installed in a vacuum deposition apparatus, and about 6 cm above the heating boat. A glass substrate (10 cm per side) was placed at the position, and the inside of the apparatus was depressurized to 10 Pa. The heating boat was heated to 200 ° C. to volatilize the curable resin composition for vapor deposition, and vapor deposited on the glass substrate. Then, the vapor-deposited glass substrate is taken out and irradiated with ultraviolet rays using an LED-UV lamp so that the irradiation amount is 3000 mJ / cm ² to cure the curable resin composition for vapor deposition to obtain a resin protective film. It was. The film thickness of the obtained resin protective film was measured with a surface roughness meter (“Dektak” manufactured by ULVAC, Inc.).

(3) Curing of the resin protective film When the surface of the resin protective film is subjected to a palpation test and it is evaluated that the surface is dried and cured, “○” indicates that it is sticky or liquid. Was evaluated as “×” to evaluate the curability of the resin protective film.

(4) Heating weight reduction rate The heating weight reduction rate was measured as an evaluation of the heat resistance of the curable resin compositions obtained in the respective Examples and Comparative Examples.
By weighing 10 mg of each of the curable resin compositions obtained in each Example and each Comparative Example in an aluminum pan and irradiating with ultraviolet rays having a wavelength of 365 nm using a high-pressure mercury lamp so that the irradiation amount is 3000 mJ / cm ^2. Cured to obtain a cured resin.
The obtained resin cured product was measured using a differential thermothermogravimetric simultaneous measurement apparatus (“EXSTAR TG / DTA7000” manufactured by Seiko Instruments Inc.), and the temperature rising rate was 10 ° C./min, 300 under an atmospheric pressure nitrogen atmosphere. The weight loss rate at ° C was determined.

(5) Total light transmittance of resin protective film The curable resin composition for vapor deposition obtained in each Example and each Comparative Example was formed to a thickness of 10 μm between two 75 mm × 25 mm × 1 mm glass plates. The resin protective film was obtained by curing by irradiating ultraviolet rays with a wavelength of 365 nm using a high pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm ² . About the obtained resin protective film, the total light transmittance was measured using the spectrophotometer (The Hitachi High-Technologies company make, "U-2900").

(6) Appearance of organic optical device The organic optical devices obtained in each Example and each Comparative Example were visually observed, and “○” indicates that no peeling or cracking was observed. The case where a crack was recognized was evaluated as “x”.

(7) Light emission state of organic optical device The organic optical device obtained in each Example and each Comparative Example was exposed for 24 hours under conditions of 25 ° C. and 50% RH, respectively, and then a voltage of 6 V was applied thereto. Visual observation of the light emission state of the device (light emission and dark spots, presence / absence of pixel periphery quenching), “○” when there was no dark spot or peripheral quenching, and even a slight dark spot or peripheral quenching was observed. Cases were evaluated as “x”.

According to the present invention, there is provided a curable resin composition for vapor deposition that can be deposited on a substrate at a low temperature and with a high vapor deposition efficiency and can form a vapor deposition film having excellent adhesion to an inorganic material film. Can do. Moreover, according to this invention, the manufacturing method of the resin protective film manufactured using this curable resin composition for vapor deposition, an organic optical device, and an organic optical device can be provided.

Claims (10)

A curable resin composition for vapor deposition that forms a vapor deposition film on a substrate by volatilization by heating under atmospheric pressure or a reduced pressure atmosphere,
A polythiol compound having two or more thiol groups in one molecule, a polyene compound having two or more carbon-carbon double bonds in one molecule, and a photopolymerization initiator,
The curable resin composition for vapor deposition, wherein the polythiol compound and the polyene compound have a molecular weight of 230 to 500. The polythiol compound and the polyene compound have a weight loss rate of 10% or less at 150 ° C. and 25% or more at 300 ° C., determined by simultaneous differential thermothermal gravimetric measurement at a heating rate of 10 ° C./min in an atmospheric pressure nitrogen atmosphere. The curable resin composition for vapor deposition according to claim 1. The curable resin composition for vapor deposition according to claim 1 or 2, wherein the ratio of the molecular weight of the polythiol compound and the polyene compound is 1: 0.5 to 1: 1.8. 4. The curable resin composition for vapor deposition according to claim 1, wherein the polyene compound contains a polyene compound having an aromatic ring. 5. The curable resin composition for vapor deposition according to claim 1, wherein the viscosity measured at 25 ° C. and 2.5 rpm using an E-type viscometer is 500 mPa · s or less. . 6. The curable resin composition for vapor deposition according to claim 5, wherein the viscosity measured under conditions of 25 ° C. and 2.5 rpm using an E-type viscometer is 200 mPa · s or less. A resin protective film obtained by photocuring the curable resin composition for vapor deposition according to claim 1, 2, 3, 4 or 5. An organic optical device comprising an organic thin film element protected by a resin protective film obtained by vapor-depositing and photocuring the curable resin composition for vapor deposition according to claim 1, 2, 3, 4 or 5. 9. The organic optical device according to claim 8, wherein an inorganic material film is further laminated on the resin protective film. A process of depositing the curable resin composition for vapor deposition according to claim 1, 2, 3, 4 or 5 on the organic thin film element, and photocuring the deposited curable resin composition for vapor deposition on the organic thin film element And a step of forming a resin protective film on the organic optical device.