KR101878117B1 - Resin composition - Google Patents

Abstract

A resin composition which can be used as a filler material when an organic EL device is sealed by a dam and fill method is excellent in coating properties and acetone solubility and can be set at arbitrary timings of thickening and curing and has a high refractive index, A resin composition capable of forming a cured product having a high melting point.
The resin composition of the present invention comprises a compound (A) represented by the following formula (a), a compound represented by the following formula (b-1), and a compound represented by the following formula (b-2) (B), and a photo cationic polymerization initiator (C).

Description

Resin composition

The present invention relates to a resin composition usable as a filler material when sealing an organic electroluminescence element by a dam and fill method. Priority is claimed on Japanese Patent Application No. 2016-074517, filed on April 1, 2016, the entire contents of which are incorporated herein by reference.

An organic EL device including an organic electroluminescence element (hereinafter sometimes referred to as " organic EL ") element has been widely used as a full-color flat panel display or as an LED It is expected as an alternative. There are two types of organic EL devices, top emission type and bottom emission type, due to differences in light extraction methods.

However, the organic EL element is more susceptible to moisture than other electronic components, and oxidation of the electrode or modification of the organic matter is caused by moisture penetrated into the organic EL element, and the emission characteristic is remarkably lowered . As a method for solving this problem, there is known a method of sealing (or covering) the periphery of the organic EL element with a low moisture-permeable resin.

As the method of sealing with the resin, there are a method (1) in which a resin composition for curing the periphery of an organic EL element formed on a substrate is cured by ultraviolet irradiation, and thereafter the resin composition is sealed by curing, (2) in which a resin composition is applied to a substrate having an organic EL device formed thereon, and the substrate is sealed after being irradiated with ultraviolet rays and then bonded to a substrate on which the organic EL device is formed.

In the method (1), there was a problem that the organic EL device was directly exposed to ultraviolet rays to lower the luminescence characteristics. In addition, when the color filter is disposed on the organic EL device in order to form the organic EL device having high contrast, ultraviolet rays are blocked by the color filter, so that the resin composition hardly hardens.

On the other hand, in the above-mentioned method (2), although it is inevitable to directly expose the organic EL element to ultraviolet rays, since the curing of the resin composition rapidly proceeds by irradiation of ultraviolet rays, , The yield was lowered.

Patent Document 1 discloses that a resin composition containing an epoxy compound, a photo cationic polymerization initiator, and a crown ether or a polyether as a curing retarder gradually undergoes a curing reaction after irradiation with ultraviolet rays. Therefore, in the method (2) It is described that the above composition can seal the organic EL device without directly exposing it to ultraviolet rays. However, crown ethers and polyethers are decomposed by acids generated from a photo cationic polymerization initiator to generate outgas, and the problem is that the organic EL element is deteriorated by the outgas.

In addition, the cured product of the resin composition is required to have a high refractive index, since it makes it difficult to generate light reflection at the interface with the organic EL element. As a resin for forming a cured product having a high refractive index, a bis (4-vinylthiophenyl) sulfide derivative is known (Patent Document 2).

Japanese Patent No. 4384509 Japanese Unexamined Patent Application Publication No. 8-183816

However, when the bis (4-vinylthiophenyl) sulfide derivative is used as a filler when the resin composition containing the bis (4-vinylthiophenyl) sulfide derivative is low in sealing the organic EL element by, for example, It was easy to flow out from the dam or the like when it was bonded to the substrate.

As a method for preventing the filler from flowing out from the dam, it is conceivable to add a polymer compound (for example, a petroleum resin or the like) excellent in the thickening effect to decrease the fluidity. However, Respectively. In addition, when the polymer compound is applied to a resin composition containing an acetone-insoluble polymer compound by using a liquid quantitative ejection device such as a dispenser, an ink-jet application device, or the like, the polymer compound is often insoluble in acetone commonly used as an industrial detergent. It was a problem that the inside of the back can not be cleaned with acetone. In addition, if it is thickened to such an extent as to prevent the outflow from the dam, it may become difficult to discharge it by using the above-mentioned apparatus or the like. Therefore, the discharge property from the apparatus or the like, the cleaning property inside the apparatus, It is very difficult to combine the anti-leakage property.

Accordingly, an object of the present invention is to provide a resin composition which can be used as a filler material when sealing an organic EL element by a dam and fill method, is excellent in coating property and acetone solubility, can set a timing of thickening and curing, Which is capable of forming a cured product having a refractive index, a low moisture permeability and a low outgassing property.

Another object of the present invention is to provide an organic EL device having a constitution in which an organic EL element is sealed by a cured product of the resin composition.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found the following.

1. A resin composition containing a phenyl sulfide compound (A) having two reactive functional groups in one molecule, a specific compound (B) having one polymerizable unsaturated group in one molecule, and a photocation polymerization initiator (C) It should have low viscosity, good applicability, and good acetone solubility.

2. When the resin composition is irradiated with ultraviolet rays, the above-mentioned (A) exhibits a curing-retarding property and at the same time, (B) exhibits a curing property, , Semi-cured state).

3. The curing reaction, which was once stopped, should be resumed by heat treatment, and then the cured product can be formed quickly.

4. The cured product shall have high refractive index, low moisture permeability and low outgassing property.

The present invention has been completed based on this finding.

That is, the present invention provides a resin composition comprising the following compound (A), the following compound (B), and a photo cationic polymerization initiator (C).

Compound (A): A compound represented by the following formula (a)

(Wherein R ^a represents a reactive functional group, R ^b is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, A carboxyl group which may be protected by a protective group, a sulfo group which may be protected by a protecting group, a nitro group, a cyano group or an acyl group which may be protected by a protective group, R ^c represents a single bond or a linking group, m represents And n represents an integer of 0 to 10. The two R ^a may be the same or different from each other. A plurality of R ^b and m may be the same or different, being)

≪ / RTI >

Compound (B): Compound (b-1) represented by the following formula

(Wherein Y represents a single bond or a linking group, and R ¹ represents a hydrogen atom or a methyl group)

, And a compound represented by the following formula (b-2)

(Wherein, R ¹ is a hydrogen atom or a methyl group, R ² represents a hydrocarbon group. T represents an integer of 0 or more, when t is 2 or more integer, a plurality of R ² may be the same, respectively, or different. When a plurality of R < ² > s exist, they may combine with each other to form a ring together with the carbon atoms constituting the aromatic ring in the formula: L represents a linking group)

≪ / RTI > or a pharmaceutically acceptable salt thereof.

The present invention also provides the above resin composition wherein R ^a in formula (a) is a vinyl group or allyl group.

The present invention also relates to a compound represented by the formula (b-2-1), wherein the compound represented by the formula (b-2)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and L represents a linking group)

Wherein R < 1 > and R < 2 >

The present invention is also characterized in that the ratio of the content of the compound (A) to the content of the compound (B) (electron: latter ratio (weight ratio)) is 60:40 to 95: 5, Wherein the resin composition contains at least 50% by weight of the total amount of the curable compound contained in the resin composition.

The present invention also provides the above resin composition wherein the viscosity at 25 캜 is 10 mPa 占 퐏 or more and less than 30 mPa 占 퐏.

The present invention also provides the resin composition as an organic electroluminescence element encapsulant.

The present invention also provides a method for producing an organic electroluminescence device, characterized in that the organic electroluminescence device is sealed through the following steps 1 and 2.

Step 1: The coating film containing the resin composition is irradiated with ultraviolet rays.

Step 2: A coating film after irradiated with ultraviolet rays obtained through Step 1 is adhered to the element mounting surface of the substrate provided with the organic electroluminescence element, and heat treatment is performed.

The present invention also provides an organic electroluminescence device having a configuration in which a device is sealed with a cured product of the resin composition.

That is, the present invention relates to the following.

[1] A process for producing a compound represented by the formula (1), comprising reacting a compound (A) represented by the formula (a) with at least one compound (B) selected from a compound represented by the formula (b- , And a photo cationic polymerization initiator (C).

[2] The resin composition according to [1], wherein R ^a in the formula (a) is a cationic polymerizable group.

[3] The resin composition according to [1], wherein R ^a in the formula (a) is ^a group selected from ^a vinyl group, an allyl group, an epoxy group, a glycidyl group and an oxetanyl group.

[4] The resin composition according to [1], wherein R ^a in the formula (a) is a vinyl group or an allyl group.

Wherein R ^c in the formula (a) is a group selected from a divalent hydrocarbon group, a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, [4] The resin composition according to any one of [1] to [4].

[6] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 1000 or less (preferably 700 or less, and most preferably 500 or less).

[7] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is from 302 to 1000 (preferably from 302 to 700, and most preferably from 302 to 500).

[8] The resin composition according to any one of [1] to [7], wherein the compound (A) is a compound represented by the formula (a ').

[9] The resin composition according to any one of [1] to [7], wherein the compound (A) is at least one compound selected from compounds represented by formulas (a'-1) to .

[10] The positive _{resist composition} as described in any one of [1] to [10], wherein Y in the formula (b-1) is a divalent hydrocarbon group (preferably a C _1-18 alkylene group, a C _2-8 alkenylene group, a C _6-10 arylene group, A resin composition according to any one of [1] to [9], wherein the group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, an amide bond, a carbonate bond,

[11] The resin according to any one of [1] to [10], wherein the compound represented by the formula (b-1) has a molecular weight of 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150) Composition.

[12] The process according to any one of [1] to [12], wherein the compound represented by the formula (b-1) is at least one selected from N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole and N- The resin composition according to any one of [1] to [11], which is a species compound.

[13] The positive _{resist composition} as described in any of [1] to [13], wherein L in the formula (b-2) is a divalent hydrocarbon group (preferably a C _1-18 alkylene group, a C _2-8 alkenylene group, a C _6-10 arylene group, 1] to [12], which is a group selected from the group consisting of a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, ≪ / RTI >

[14] The resin according to any one of [1] to [13], wherein the compound represented by the formula (b-2) has a molecular weight of 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150) Composition.

[15] The resin composition according to any one of [1] to [14], wherein the compound represented by the formula (b-2) is a compound represented by the formula (b-2-1).

The content of the compound (A), the compound (B) and the compound other than the photocation polymerization initiator (C) is preferably 40% by weight or less (preferably 20% by weight or less, particularly preferably 10% (1) to (15).

The total content of the compound (A), the compound (B) and the cationic photopolymerization initiator (C) is preferably 60 wt% or more (preferably 80 wt% or more, particularly preferably 90 wt% , The resin composition according to any one of [1] to [16].

[18] The polymer composition according to any one of [1] to 5, wherein the content of the polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5,000, particularly preferably more than 10,000) is 5% by weight or less (preferably 3% ) The resin composition according to any one of [1] to [17].

The content of the compound having a solubility parameter (SP value at 25 ° C: value calculated in Fedors' formula) of 8.5 or more is 5 wt% or less (preferably 3 wt% or less, particularly preferably 1 wt% or less) , And the resin composition according to any one of [1] to [18].

[20] A polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5,000, particularly preferably more than 10,000) and a compound having a solubility parameter (SP value at 25 ° C; The resin composition according to any one of [1] to [19], wherein the content is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less).

The ratio of the content of the compound (A) to the content of the compound (B) (electron: latter ratio (weight ratio)) is 60:40 to 95: 5 (preferably 65:35 to 90:10, 30 to 85:15), and the total content of the compound (A) and the compound (B) accounts for at least 50% by weight (preferably at least 60% by weight, more preferably at least 70% by weight %, More preferably not less than 80 wt.%, Most preferably not less than 90 wt.% Of the total weight of the resin composition.

The content of the compound (A) in the resin composition is preferably 45 to 95% by weight (preferably 60 to 95% by weight, more preferably 65 to 90% by weight, particularly preferably 60 to 95% by weight) of the total amount of the curable compound , Preferably 70 to 85% by weight, based on the total weight of the resin composition.

It is preferable that the content of the compound (B) is 5 to 40% by weight (preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight) of the total amount of the curing compound (100% , And the resin composition according to any one of [1] to [22].

The content of the photo cationic polymerization initiator (C) is preferably 0.01 to 15 parts by weight (preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, more preferably 0.05 to 5 parts by weight) relative to 100 parts by weight of the curable compound contained in the resin composition. And most preferably 0.1 to 3 parts by weight based on 100 parts by weight of the resin composition.

[25] The resin composition according to any one of [1] to [24], wherein the viscosity at 25 ° C. in the case of unirradiated ultraviolet radiation is 10 mPa · s or more and less than 30 mPa · s (preferably 15 to 25 mPa · s) .

[26] The ultraviolet ray irradiation: to any one of [1] to [25] (dose 1500mJ / cm ²⁾ have a viscosity at 25 ℃ just after 30 to 2000mPa · s (preferably 30 to 1000mPa · s) ≪ / RTI >

[27] Any of [1] to [26], which has a viscosity at 25 ° C. of 30 to 2500 mPa · s (preferably 30 to 1500 mPa · s) for 30 minutes after irradiation with ultraviolet light (irradiation amount: 1500 mJ / cm ² ) Lt; / RTI >

[1] to [3], wherein the viscosity (viscosity after 30 minutes of ultraviolet irradiation / viscosity immediately after ultraviolet irradiation) of the viscosity immediately after ultraviolet irradiation and after 30 minutes of ultraviolet irradiation is 1.30 or less [27] The resin composition described in any one of [1] to [27].

[29] The resin composition according to any one of [1] to [28], which is an organic electroluminescence element encapsulant.

[30] A method for manufacturing an organic electroluminescent device, characterized in that the organic electroluminescence device is sealed through the following steps 1 and 2.

Step 1: A coating film containing the resin composition according to any one of [1] to [29] is irradiated with ultraviolet rays.

Step 2: A coating film after irradiated with ultraviolet rays obtained through Step 1 is adhered to the element mounting surface of the substrate provided with the organic electroluminescence element, and heat treatment is performed.

[31] An organic electroluminescence device having a configuration in which a device is sealed with a cured product of the resin composition according to any one of [1] to [29].

[32] The organic electroluminescence device according to [31], wherein the cured product is a cured product having a refractive index of 1.65 or more (preferably 1.68 or more) with respect to light having a wavelength of 589.3 nm at 25 ° C.

The cured product preferably has a water vapor permeability (g / m ² · day · atm) of 100 or less (preferably 50 or less, particularly preferably 35 or less, most preferably 25 or less) The organic electroluminescence device according to [31] or [32], which is a cured product.

The cured product is a cured product having an outgassing amount of 60 mg of the cured product of not more than 1000 ppm (preferably not more than 200 ppm, particularly preferably not more than 100 ppm). The organic electroluminescent device according to any one of [31] to [ Sense device.

Since the resin composition of the present invention has the above-described constitution, the resin composition is excellent in fluidity at a low point until irradiation with ultraviolet rays, and can be satisfactorily discharged by using a liquid metering device. In addition, since it exhibits excellent solubility in acetone used as an industrial detergent, it is possible to easily clean the interior of the apparatus and the like using acetone. When the resin composition of the present invention is used as a filler when sealing the organic EL element by, for example, a dam-and-filing method, ultraviolet rays are irradiated after being discharged into a dam , It is possible to prevent the leakage from the dam. In addition, even when ultraviolet rays are irradiated, the progress of the curing reaction can be stopped in the semi-cured state until the heat treatment is performed, and the timing of the curing reaction can be arbitrarily set by adjusting the timing of performing the heat treatment. The cured product can be quickly cured by applying a heat treatment after ultraviolet irradiation to form a cured product having a high refractive index, a low moisture permeability and a low outgassing property.

Therefore, by irradiating the resin composition of the present invention with ultraviolet light, bonding it to a substrate provided with the organic EL device, and then performing heat treatment after bonding, it is possible to prevent the leakage from the dam and to make the bonding difficult The sealing operation can be performed. Thus, the organic EL element can be sealed with a cured product having high refractive index, low moisture permeability, and low outgassing property without directly exposing the organic EL element to ultraviolet rays.

Therefore, the resin composition of the present invention is preferably used particularly as a sealing agent (in particular, a filler) of a top-emission type organic EL device, a light-emitting layer material of a bottom-emission type organic EL device, a solar cell material, .

In particular, when the resin composition of the present invention is used as a sealing agent, an organic EL device having excellent light extraction efficiency, high efficiency, high brightness and long life can be obtained. Further, when the resin composition of the present invention is used as a lens material, a lens having a high refractive index can be obtained, the lens can be made thinner and lighter, and the designability of an electronic device including the lens can be improved.

1 is a schematic view showing an example of a method for producing an organic EL device using the resin composition of the present invention.

[Compound (A)]

The compound (A) in the present invention is a compound (curable compound) represented by the above formula (a). Two R ^a in the formula (a) represent a reactive functional group (polymerizable functional group). The two R ^a may be the same or different. Examples of the reactive functional group include a cationic polymerizable group such as a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group. In the present invention, a vinyl group or an allyl group is particularly preferable.

A plurality of R ^b in formula (a) are the same or different and each represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, An amino group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, a sulfo group which may be protected with a protecting group, a nitro group, a cyano group or an acyl group which may be protected with a protecting group.

Examples of the halogen atom in R ^b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group in R ^b include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t- butyl group, a hexyl group, a heptyl group, , A C _1-10 (preferably C _1-5 ) alkyl group such as a decyl group, and the like. Examples of the haloalkyl group for R ^b include a C _1-10 (preferably C _1-5 ) haloalkyl group such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. have. Examples of the aryl group in R ^b include a phenyl group and a naphthyl group. Further, the aromatic ring of the aryl group may be substituted with a halogen such as a halogen atom such as a fluorine atom, a C _1-5 haloalkyl group such as a C _1-4 alkyl group such as a methyl group, a trifluoromethyl group, a C _1-5 haloalkyl group such as a hydroxyl group, _1-4 alkoxycarbonyl group, an amino group, a dialkylamino group, a carboxyl group, a methoxycarbonyl group, such as a C _1-4 alkoxycarbonyl group, a nitro group, a cyano group, an acetyl group or the like of an acyl group (particularly, C _1-6 aliphatic acyl group), etc. May have a substituent of

As the hydroxyalkyl group for R ^b , for example, a C _1-10 (preferably C _1-5) alkyl group in which at least one of the hydrogen atoms of the C _1-10 alkyl group such as a hydroxymethyl group is substituted with a hydroxyl group ) Hydroxyalkyl group and the like. Examples of the protecting group for the hydroxyl group and the protecting group for the hydroxyalkyl group in R ^b include protecting groups for common use in the field of organic synthesis (for example, alkyl groups (e.g., C _1-4 alkyl groups such as methyl and t- Etc); An alkenyl group (e.g., an allyl group and the like); A cycloalkyl group (e.g., cyclohexyl group and the like); An aryl group (e.g., 2,4-dinitrophenyl group and the like); Aralkyl groups (e.g., benzyl group and the like); (E.g., methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl and the like), substituted ethyl groups (for example, 1-ethoxyethyl group and the like) A group capable of forming an acetal or hemiacetal group with a hydroxyl group such as a tetrahydropyranyl group, a tetrahydrofuranyl group, a 1-hydroxyalkyl group (for example, 1-hydroxyethyl group and the like); An acyl group (for example, a C _1-6 aliphatic acyl group such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group or pivaloyl group, an acetoacetyl group, an aromatic acyl group such as benzoyl group, ; An alkoxycarbonyl group (e.g., a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group and the like); An aralkyloxycarbonyl group; A substituted or unsubstituted carbamoyl group; Substituted silyl groups (e.g., trimethylsilyl group and the like); When two or more hydroxyl groups or hydroxymethyl groups are present in the molecule, a divalent hydrocarbon group which may have a substituent (for example, a methylidene group, an ethylidene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group , Benzylidene group, etc.)].

As the protecting group for the amino group in R ^b , there can be mentioned a protecting group (for example, an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group and the like exemplified as a protecting group of the above-mentioned hydroxyl group) in the field of organic synthesis.

Examples of the protective group of the carboxyl group and the sulfo group in R ^b include a protecting group which is common in the field of organic synthesis (for example, an alkoxy group (for example, a C _1-6 alkoxy group such as methoxy, ethoxy, And the like), a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, a trialkylsilyloxy group, an amino group which may have a substituent, a hydrazino group, an alkoxycarbonylhydrazino group, an aralkylcarbonylhydrazino group and the like ].

Examples of the acyl group in R ^b include C _1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group and pivaloyl group; Acetoacetyl group; And an aromatic acyl group such as benzoyl group. As the protecting group of the above-mentioned acyl group, a protecting group can be used in the field of organic synthesis. Examples of the protected form of the acyl group include acetal (including hemiacetal) and the like.

When a plurality of R ^b is bonded to one aromatic ring in formula (a) (that is, when m in formula (a) is 2 to 4), two or more groups selected from the plurality of R ^b bond to each other (For example, alicyclic carbon rings such as a 5-membered alicyclic carbon ring, a 6-membered alicyclic carbon ring, and a condensed ring of 2 or more alicyclic carbon ring (monocyclic ring)) together with a carbon atom constituting an aromatic ring A 5-member lactone ring, a 6-member lactone ring, or the like) may be formed.

R ^c in the formula (a) represents a single bond or a linking group (bivalent group having at least one atom). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-) ), A carbonate bond (-OCOO-), and a group in which a plurality of these are bonded. The linking group may have a substituent such as a hydroxyl group or a carboxyl group. Examples of such linking group include a divalent hydrocarbon group having at least one hydroxyl group.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3- A cycloalkylene group (including a cycloalkylidene group) such as a 1,4-cyclohexylene group, and a cyclohexylidene group.

The molecular weight of the compound (A) is not particularly limited, but is preferably 1,000 or less, particularly preferably 700 or less, and most preferably 500 or less, from the viewpoint of compatibility with the compound (B). The lower limit of the molecular weight is 302.

A plurality of m in the formula (a) are the same or different and represent an integer of 0 to 4; Furthermore, n (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.

Among them, n in the formula (a) is preferably 0 to 3, and particularly preferably 0 because the viscosity of the resin composition can be controlled within a wide range. That is, as the compound (A), a compound represented by the following formula (a ') is particularly preferable.

(Wherein R &^lt; ^a & gt ^; , R &^lt; ^b & gt ^; , and m are as defined above)

Examples of the compound (A) include compounds represented by the following formulas (a'-1) to (a'-12).

The compound (A) can be produced by a known or common method. For example, a method of reacting vinylidene halide, halogenated allyl, halide of (meth) acrylic acid, epihalohydrin or the like with 4,4'-thiobisbenzenethiol or the like as a raw material in the presence of a base . The compound in which R ^a in the formula (a) is a vinyl group can also be prepared by reacting 4,4'-thiobisbenzenethiol with a dihaloethane, followed by conversion into a dehydrohalogenated hydrogen.

The compound (A) has a low viscosity and is excellent in acetone solubility. In addition, curing is delayed by capturing an acid generated from the photo cationic polymerization initiator (C) by ultraviolet irradiation. When irradiated with ultraviolet rays and then subjected to a heat treatment, the compound (A) rapidly releases the captured acid and cures to form a cured product having a high refractive index, a low moisture permeability and a low outgassing property.

[Compound (B)]

The compound (B) in the present invention includes at least one compound selected from the compounds (b-1) and (b-2).

(Compound (b-1))

The compound (b-1) in the present invention is a compound (a cation and a radically polymerizable compound) represented by the following formula (b-1). The compound (b-1) is rapidly polymerized by the acid generated from the photo cationic polymerization initiator (C). Therefore, the polymerization reaction can be allowed to proceed for a little time until the compound (A) captures the acid generated from the photo cationic polymerization initiator (C). When the photo cationic polymerization initiator (C) is irradiated with ultraviolet light, the photo cationic polymerization initiator (C) absorbs ultraviolet light to decompose to form a radical, and the radical exits hydrogen to generate an acid. The compound (b-1) can also react with the radicals to proceed the polymerization reaction. Therefore, even in the presence of the compound (A) having an action of capturing an acid generated from the photo-cationic polymerization initiator (C), the polymerization reaction can be promoted to some extent and the resin composition of the present invention is in a semi-cured state Lt; / RTI >

(Wherein Y represents a single bond or a linking group, and R ¹ represents a hydrogen atom or a methyl group)

Wherein Y represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (-CO-), an ether linkage (-O-), an ester linkage (-COO-), an amide linkage (-CONH-), a carbonate linkage -) and a group in which a plurality of these are connected. As the bivalent hydrocarbon group, for example, a linear or branched alkylene group having 1 to 18 carbon atoms; Chain or branched alkyl group having 2 to 8 carbon atoms such as a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, An alkenylene group; A divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms (e.g., phenylene group), and a group bonded via a single bond.

The molecular weight (or weight average molecular weight) of the compound (b-1) is, for example, about 1000 to 70 (preferably 700 to 100), particularly preferably 400 to 150, It is preferable in terms of being capable of having fluidity. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

Examples of the compound (b-1) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole and N- (vinylbenzyl) carbazole. These may be used singly or in combination of two or more.

(Compound (b-2))

The compound (b-2) in the present invention is a compound (radically polymerizable compound) represented by the following formula (b-2). When the photo cationic polymerization initiator (C) is irradiated with ultraviolet light, the photo cationic polymerization initiator (C) absorbs ultraviolet light to decompose to form a radical, and the radical exits hydrogen to generate an acid. -2), the curing reaction proceeds by reacting with the radicals to induce the resin composition of the present invention to a semi-cured state.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group. t represents an integer of 0 or more, and when t is an integer of 2 or more, plural R ² may be the same or different. When a plurality of R ^{2 s} exist, they may be bonded to each other to form a ring with the carbon atoms constituting the aromatic ring in the formula. L represents a linking group.

The hydrocarbon group in R < ² > includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group bonded thereto.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t- An alkyl group having from 1 to 20 (preferably from 1 to 10, more preferably from 1 to 3) carbon atoms; An alkenyl group having 2 to 20 (preferably 2 to 10, more preferably 2 to 3) carbon atoms such as a vinyl group, an allyl group and a 1-butenyl group; An alkynyl group having 2 to 20 (preferably 2 to 10, more preferably 2 to 3) carbon atoms such as an ethynyl group and a propynyl group.

Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 3 to 20 atoms (preferably 3 to 15 atoms, more preferably 5 to 20 atoms) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, 8-membered) cycloalkyl group; A cycloalkenyl group of about 3 to 20 atoms (preferably about 3 to 15 atoms, more preferably about 5 to 8 atoms) such as a cyclopentenyl group and a cyclohexenyl group; And bridged cyclic hydrocarbon groups such as a perhydronaphthalene-1-yl group, a norbornyl group, an adamantyl group and a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-3-yl group.

Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms) such as a phenyl group and a naphthyl group.

In the case where a plurality of R ^{2 s} in the formula (b-2) are present, the ring which may be bonded together with the carbon atom constituting the aromatic ring in the formula may be, for example, Aromatic carbocyclic ring or 3 to 20 membered non-aromatic heterocyclic ring.

The hydrocarbon group may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a C _1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group.

As R ² in the above formula (b-2), an aromatic hydrocarbon group is particularly preferable.

T in the formula (b-2) represents an integer of 0 or more. t is, for example, an integer of 0 to 3, preferably an integer of 1 or more (for example, an integer of 1 to 3).

L represents a linking group. The linking group is a divalent group having at least one atom and is, for example, a divalent hydrocarbon group, a carbonyl group (-CO-), an ether linkage (-O-), a thioether linkage (-S-), an ester linkage -), an amide bond (-CONH-), a carbonate bond (-OCOO-), and a group in which a plurality of them are connected. Examples of the bivalent hydrocarbon group include the same examples as those in Y in the above formula (b-1).

The molecular weight (or weight average molecular weight) of the compound (b-2) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150) It is preferable in that it can be provided. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The compound (b-2) is preferably a compound represented by the following formula (b-2) in view of being capable of forming a cured product having excellent compatibility with the above-mentioned compound (A) and having high refractive index, low moisture- -2-1) is preferred. In the formula, R ¹ and L are as defined above.

The resin composition of the present invention contains at least one compound selected from the compound (b-1) and the compound (b-2) as the compound (B) together with the compound (A). When the resin composition of the present invention is irradiated with ultraviolet rays, the compound (A) captures an acid generated from the photo cationic polymerization initiator (C) and exhibits a curing-retarding property, while the compound (B) Since the reaction proceeds, the action of these is combined, resulting in a semi-cured state.

The compound (B) in the present invention is low in viscosity and excellent in acetone solubility. Further, a cured product having a high refractive index, a low moisture permeability and a low outgassing property can be formed by curing.

[Photo cationic polymerization initiator (C)]

The photo cationic polymerization initiator is a compound which decomposes by irradiation with ultraviolet rays to form a radical form, and the radical forms a hydrogen atom to generate an acid to initiate the curing reaction of the curable compound. The photo cationic polymerization initiator includes a cation moiety for absorbing light and an anion moiety for generating an acid.

Examples of the photo cationic polymerization initiator of the present invention include a diazonium salt compound, an iodonium salt compound, a sulfonium salt compound, a phosphonium salt compound, a selenium salt compound, an oxonium salt compound, an ammonium salt compound, .

Among them, it is preferable to use a sulfonium salt-based compound because a cured product having excellent curability can be formed. Examples of the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, And arylsulfonium ions such as tolylsulfonium ions (particularly, triarylsulfonium ions).

Examples of the anion moiety of the photo cationic polymerization initiator include BF ₄ ^- , B (C ₆ F ₅ ) ₄ ^- , PF ₆ ^- , [(Rf) _k PF _6-k ] ^- (R f: K is an integer of 1 to 5), AsF ₆ ^- , SbF ₆ ^- , SbF ₅ OH ^- and the like.

Examples of the photo cationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) (Pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexa (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (Pentafluoroethyl) trifluorophosphate, trade name " Sara Cure UVI-6970 ", " Sara Cure " UG-6990 ", " SAIRACURE UVI-950 " (manufactured by Union Carbide Corporation), Irgacure 250, Irgacure 261, ADEKA OPTOMER SP-150 ", " Adeka Optomer SP-151 ", " Adeka Optomer SP-170 ", & (Manufactured by BASF), "DAICAT II" (manufactured by Daicel), "UVAC 1590", "UVAC 1591" CI-2655 "," CI-2481 "," CI-2734 "," CI-2855 "," PI-2074 "(manufactured by Rhodia), tetrakis (pentafluorophenyl borate) tolylcumyl iodide (trade name, manufactured by Nippon Soda Co., Ltd.)," CI-2823 "," CI-2758 " "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103" CD-1010 "," CD-1012 "(manufactured by Sartomer Co., Ltd., USA)," DTS-103 "," NAT-103 "," NDS- Quot; CPI-100P ", and " CPI-101A " (manufactured by San Aipro Co., Ltd.) can be used.

[Other additives]

The resin composition of the present invention may further contain a curing compound (excluding the compounds (A) and (B)), filler, silane coupling agent, polymerization inhibitor, antioxidant, light stabilizer, plasticizer, An antioxidant, a leveling agent, a defoaming agent, a pigment, an organic solvent, an ultraviolet absorber, an ion adsorbent, a fluorescent substance, a release agent, and a rheology control agent. The content thereof is, for example, not more than 40% by weight, preferably not more than 20% by weight, particularly preferably not more than 10% by weight, based on the total amount of the resin composition. The resin composition of the present invention is preferably a polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and / or a solubility parameter (SP value at 25 캜; Fedors , The content thereof is, for example, not more than 5% by weight, preferably not more than 3% by weight, particularly preferably not more than 1% by weight. When the content of the polymer compound exceeds the above range, the acetone solubility is lowered, and it is not preferable because it is difficult to clean the inside of the liquid quantitative ejection apparatus with acetone.

The resin composition of the present invention may contain a polymerization initiator other than the photo cationic polymerization initiator (C) (for example, photo radical polymerization initiator and the like), but the resin composition of the present invention may contain The proportion of the cationic photopolymerization initiator (C) is, for example, at least 60% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight. The upper limit is 100% by weight. The content of the photo-radical polymerization initiator in the resin composition of the present invention is 10% by weight or less (particularly 5% by weight or less, particularly 1% by weight or less) of the total amount of the polymerization initiator contained in the resin composition of the present invention, , And it is most preferable that it is substantially not included. If the content of the photo radical polymerization initiator exceeds the above range, the viscosity after irradiation with ultraviolet rays becomes too high, and it tends to be difficult to maintain the adhesiveness.

≪ Resin composition and method for producing the same &

The resin composition of the present invention can be produced by homogeneously mixing the above-mentioned compound (A), compound (B), photo cationic polymerization initiator (C) and other components as necessary. Each of the compound (A), the compound (B) and the photo cationic polymerization initiator (C) may be used alone or in combination of two or more. In obtaining the resin composition of the present invention, each component is as uniform as possible by using a generally known mixing apparatus such as a self-propelled type stirring defoaming device, a homogenizer, a planetary mixer, a three-axis roll mill or a bead mill Stirring, dissolving, mixing, dispersing, and the like. The respective components may be mixed at the same time or may be mixed in order.

The content of the compound (A) in the resin composition of the present invention is, for example, 45 to 95% by weight, preferably 60 to 95% by weight, more preferably 60 to 95% by weight of the total amount of the curing compound (100% By weight is 65 to 90% by weight, particularly preferably 70 to 85% by weight.

The content of the compound (B) in the resin composition of the present invention is, for example, 5 to 40% by weight, preferably 10 to 35% by weight, more preferably 10 to 30% by weight, of the total amount of the curing compound (100% Particularly preferably 15 to 30% by weight.

The ratio of the content of the compound (A) to the content of the compound (B) (electron: latter ratio (weight ratio)) in the resin composition of the present invention is, for example, 60:40 to 95: 5, To 90:10, particularly preferably from 70:30 to 85:15.

The total content of the compound (A) and the compound (B) in the resin composition of the present invention is, for example, not less than 50% by weight, preferably not less than 60% by weight of the total amount of the curing compound (100% By weight, more preferably not less than 70% by weight, particularly preferably not less than 80% by weight, particularly preferably not less than 90% by weight. The upper limit is 100% by weight.

The content of the photo cationic polymerization initiator (C) in the resin composition of the present invention is, for example, preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight per 100 parts by weight of the curing compound contained in the resin composition Particularly preferably 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight.

Since the resin composition of the present invention contains the compound (A) and the compound (B) in the above-mentioned ranges as the curable compound, the fluidity is appropriately lowered by irradiation with ultraviolet rays to induce a semi-cured state, . Therefore, when the resin composition of the present invention is used, for example, as a filler, leakage from the dam can be prevented. In addition, even when irradiated with ultraviolet rays, it is possible to maintain the semi-cured state (i.e., maintaining the adhesiveness) until the heat treatment is performed, and the timing of the curing reaction can be arbitrarily set by adjusting the timing of the heat treatment. When the content of the compound (A) is less than the above range (or the content of the compound (B) exceeds the above range), the viscosity after irradiation with ultraviolet rays becomes too high, A gap is formed between the substrate and the bonded substrate, and the sealing accuracy tends to be lowered. On the other hand, if the content of the compound (A) exceeds the above range (or the content of the compound (B) falls below the above range), the fluidity can not be lowered even when irradiated with ultraviolet rays. There is a case that it is difficult to prevent the outflow from the dam.

The resin composition of the present invention is excellent in flowability until irradiated with ultraviolet rays and has a viscosity at 25 占 폚 of, for example, 10 mPa 占 퐏 or more and less than 30 mPa 占 퐏, preferably 15 to 25 mPa 占 퐏. For this reason, it is possible to satisfactorily discharge the ink using a liquid constant-quantity discharging device such as a dispenser or an ink-jet applying device. The viscosity of the resin composition can be measured using an E-type viscometer or a rheometer.

The resin composition of the present invention comprises a compound (A) having an effect of capturing an acid generated from a photo cationic polymerization initiator (C) and inhibiting the progress of the curing reaction, and a decomposition product of the acid or photo cationic polymerization initiator (C) (B) in which the curing reaction proceeds by the radical form, when the ultraviolet ray irradiation is performed, the curing reaction of the compound (B) is limited to such a degree that the fluidity is lowered and the curing does not proceed until the adhesiveness is lost Do not. In other words, the semi-cured state is maintained by exhibiting the hardening-retarding property.

Since the resin composition of the present invention can appropriately lower the fluidity by irradiating ultraviolet rays, it is not necessary to add a polymer compound (for example, a petroleum resin or the like) generally used for the purpose of imparting a thickening property . Therefore, the acetone solubility is excellent. It is also possible to prevent the generation of outgas originating from additives.

The ultraviolet irradiation preferably irradiates light of 1000 mJ / cm ² or more with a mercury lamp or the like.

The viscosity of the resin composition immediately after irradiation with ultraviolet light (irradiation amount: 1500 mJ / cm ² ) at 25 캜 is, for example, 30 to 2,000 mPa · s, preferably 30 to 1,000 mPa · s.

Further, the resin composition of the present invention it is possible to maintain a semi-cured state until it is subjected to too, the heat treatment to investigate the UV rays, UV irradiation (dose: 1500mJ / cm ²⁾ at 25 ℃ of the resin composition in 30 minutes For example, 30 to 2500 mPa · s, and preferably 30 to 1500 mPa · s. That is, the resin composition of the present invention is excellent in the curing retarding effect and has an increase in viscosity (= viscosity after 30 minutes of UV irradiation / ultraviolet irradiation after UV irradiation) for 30 minutes after irradiation of ultraviolet rays, For example, it can be kept at 1.30 or less, preferably at 1.20 or less.

The resin composition of the present invention resumes the curing reaction by releasing an acid trapped in the compound (A) after irradiation with ultraviolet rays, followed by heat treatment, and the cured product can be formed quickly after the heat treatment.

The heat treatment is carried out at a temperature of, for example, 50 to 200 DEG C (more preferably 50 to 170 DEG C, and preferably 50 to 150 DEG C) for 10 to 600 minutes (more preferably 10 to 360 minutes, For 15 to 180 minutes).

Since the resin composition of the present invention has the above characteristics, when the resin composition is used as an encapsulant of an organic EL device, the resin composition that has been subjected to ultraviolet irradiation in advance and has reduced fluidity is applied to the organic EL device, It is possible to bond the organic EL element to the organic EL element while preventing the organic EL element from being directly exposed to ultraviolet rays.

<Hard goods>

The cured product of the resin composition of the present invention can be obtained by subjecting the resin composition to ultraviolet irradiation under the above-described conditions and further subjecting it to heat treatment under the above-described conditions.

The refractive index of the cured product of the resin composition of the present invention with respect to light (sodium D line) at a wavelength of 589.3 nm at 25 DEG C is, for example, 1.65 or more, preferably 1.68 or more. The refractive index of the cured product can be measured by, for example, a method according to JIS K 7142 or a method using a prism coupler.

The moisture permeability (g / m ² · day · atm) of the cured product (thickness: 100 μm) is, for example, not more than 100, preferably not more than 50, particularly preferably not more than 35 Or less, and most preferably 25 or less. The moisture permeability is a value obtained by measuring the moisture permeability of the cured product adjusted to 100 탆 in thickness under the conditions of 60 캜 and 90% RH in accordance with JIS L 1099 and JIS Z 0208.

Further, the cured product has a low outgassing property, and the amount of outgas of the cured product (60 mg) is, for example, 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less). The amount of outgas can be measured by headspace GC / MS.

As described above, the resin composition of the present invention has a low viscosity until irradiation with ultraviolet rays, and is excellent in coatability and acetone solubility. In addition, by irradiating ultraviolet rays, the fluidity can be suitably lowered to a semi-cured state, and the semi-cured state can be maintained until the heat treatment is performed. The curing reaction can be resumed by irradiating ultraviolet rays and then heat treatment, and then cured rapidly to form a cured product having high refractive index, low moisture permeability and low outgassing property. Therefore, for example, it is preferable to use a sealing agent (in particular, a filler) of a top emission type organic EL device, a light-emitting layer material of a bottom-emission type organic EL device, a solar cell material, a lens material (in particular, a high refractive index lens material) Can be used. Particularly, when the resin composition of the present invention is used as a sealing agent in the process of producing an organic EL device, reflection of light at the interface with the high refractive index member can be suppressed, light extraction efficiency can be improved, , A high luminance, and a long life can be obtained.

&Lt; Organic EL Device Manufacturing Method >

The method for manufacturing an organic EL device of the present invention is characterized by sealing an organic EL element (in particular, a top-emission type organic EL element) through the following steps 1 and 2.

Step 1: The coating film containing the resin composition described above is irradiated with ultraviolet rays.

Step 2: A coating film after irradiated with ultraviolet rays obtained through Step 1 is adhered to the element mounting surface of the substrate on which the organic EL element is provided, and heat treatment is performed.

According to the manufacturing method of the present invention, it is possible to seal the organic EL element while preventing deterioration of the element by ultraviolet irradiation, and it is possible to provide an organic EL device with long life and high reliability. The ultraviolet ray irradiation and heat treatment method can be carried out by the same method as the ultraviolet ray irradiation and heat treatment of the resin composition described above.

As the production method of the present invention, more specifically, the following method 1 can be mentioned.

&Lt; Method 1: See Fig. 1 &

Step 1-1: A coating film / lead laminate is formed by coating the above-mentioned resin composition on a lead.

Process 1-2: The coating film is irradiated with ultraviolet rays.

Step 2-1: An organic EL element is provided on a substrate, and a coating film / lead laminate after irradiation with ultraviolet rays is bonded to the organic EL element mounting surface so that the coating film surface is opposed to the element mounting surface.

Step 2-2: Heat treatment is performed to cure the coating film.

As the lead (lid) and the substrate, it is preferable to use a moisture-proof substrate, for example, a glass substrate such as soda glass or alkali-free glass; Metal substrates such as stainless steel and aluminum; Polyfluorinated ethylene polymers such as polytetrafluoroethylene, polytetrafluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), copolymers of PCTFE and PVDF, copolymers of PVDF and polyfluoroethylene chloride, polyimide, Cycloolefin resins such as polycarbonate and dicyclopentadiene, polyesters such as polyethylene terephthalate, and resin materials such as polyethylene and polystyrene. The same substrate may be used for the leads and the substrate. In this case, the side where the organic EL element is provided is referred to as a substrate, and the side where the organic EL element is not provided is referred to as a lead.

The organic EL element includes a laminate of an anode / a light emitting layer / a cathode. A passivation film such as a SiN film may be provided as needed.

The coating film containing the resin composition of the present invention can be obtained by, for example, applying a dam material onto a lead (lid) to form a dam, and using the liquid quantum discharge device such as a dispenser or an ink- As shown in Fig. The thickness of the coating film is not particularly limited as long as it can achieve the purpose of protecting the organic EL element from moisture and the like. Further, since the resin composition of the present invention is excellent in acetone solubility, the inside of the apparatus and the like can be easily cleaned using acetone.

According to the above method, since the fluidity of the resin composition is appropriately lowered by irradiating the coating film containing the resin composition of the present invention with ultraviolet rays, the resin composition is bonded to the organic EL element, thereby preventing the resin composition from flowing out from the dam can do. Further, by performing heat treatment after bonding, the organic EL element can be sealed without being exposed to ultraviolet rays, and the organic EL element does not have deterioration due to ultraviolet rays. Further, since the curing reaction is resumed by performing the heat treatment after the bonding, even if the bonding operation is delayed, the bonding is not difficult. The organic EL device can be protected by sealing the organic EL device with a cured product having high refractive index, low moisture permeability and low outgassing property. Therefore, the organic EL device obtained by sealing the organic EL element by the above method has a long life and high reliability.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The viscosity of the resin composition is a value measured at 25 ° C and a shear rate of 20 (1 / s), as measured using a rheometer (trade name "Physica MCR301", manufactured by Anton Paar). Examples 6 and 7 are described as reference examples.

Production Example 1

Sodium hydride (containing 55% by weight of mineral oil) (15.4 g, 352.9 mmol) and DMSO (510.6 g) were placed in a 2 L four-necked flask equipped with a stirrer, a condenser and a thermometer, Then, a solution of o-phenylphenol (50.6 g, 297.3 mmol) dissolved in DMSO (191.0 g) was added dropwise thereto. Thereafter, a solution obtained by dissolving 2-chloroethyl vinyl ether (38.2 g, 358.5 mmol) in DMSO (61.4 g) was added dropwise into an oil bath at 60 ° C. The reaction solution was stirred for 6 hours, cooled to 0 占 폚, slowly dropped by water, and transferred to a separating funnel. The aqueous layer was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Thereafter, the organic layer was separated, dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain a liquid crude product. This was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1 (volume ratio)) to obtain 55.5 g of (2-phenylphenoxy) ethyl vinyl ether represented by the following formula 98%) as a colorless transparent liquid.

^{1 H-NMR (500MHz, CDCl} 3): δ 3.96 (t, J = 5.0Hz, 2H), 4.17-4.21 (m, 3H), 6.44 (dd, J = 14.1, 6.5Hz, 1H), 6.98-7.01 (m, 1H), 7.04-7.07 (m, 1H), 7.28-7.41 (m, 6H), 7.56-7.57

Example 1

MPV (82 parts by weight), VCZ (17 parts by weight), and photo cationic polymerization initiator (1 part by weight) were charged into a self-propelled type stirring defoaming apparatus (AR-250, manufactured by Shinki) To obtain a composition (1).

The obtained resin composition (1) was molded into a mold, and irradiated with ultraviolet rays (irradiation amount: 1500 mJ / cm ² ) at a distance of 10 cm with a high-pressure mercury lamp of 200 W / cm.

The obtained resin composition (1) was measured for viscosity before UV irradiation, immediately after UV irradiation, and after UV irradiation for 30 minutes, and the degree of viscosity increase after ultraviolet irradiation was calculated from the following formula.

Viscosity increase after ultraviolet irradiation = Viscosity after 30 minutes of UV irradiation / Viscosity immediately after ultraviolet irradiation

The resin composition (1) after irradiation with ultraviolet rays was subjected to heat treatment (100 占 폚, 1 hour) to obtain a cured product (1) (thickness: 100 占 퐉).

Examples 2 to 7 and Comparative Examples 1 to 3

A resin composition and a cured product were prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in the following table.

&Lt; Acetone Solubility >

100 mL of acetone was added to 1 g of the resin composition obtained in Examples and Comparative Examples, and the acetone solution obtained by stirring the mixture at 25 DEG C for 1 hour using a magnetic stirrer bar was visually checked for transparency, Respectively.

&Lt; Drain prevention property from dam &

Manufacture of UV delay-hardening dam material

30 parts by weight of (3,4,3 ', 4'-diepoxy) bicyclohexyl, 70 parts by weight of liquid bisphenol F diglycidyl ether (trade name: YL-983U, manufactured by Mitsubishi Chemical Corporation) - (4-biphenylylthio) phenyl-4-biphenylyl phenylsulfonium tetrakis (pentafluorophenyl) borate, 1,3,4,6-tetraglycidyl glycoluril (trade name: TG , 2.5 parts by weight of talc (average particle diameter 1.5 占 퐉, flat plate particle, trade name "FG-15", manufactured by Nippon Talc Co., Ltd.) , 0.5 part by weight of an inorganic filler (average particle diameter 15 mu m, trade name &quot; SD-DB &quot;, manufactured by Hayakawa Rubber Co., Ltd.) was charged into a self- Damping material was obtained.

The viscosity of the obtained UV delay-curable dam material was 150 Pa · s. The viscosity of the UV delay curable damping material immediately after irradiation with ultraviolet rays (irradiation amount: 1500 mJ / cm ² ) at a distance of 10 cm with a high-pressure mercury lamp of 200 W / cm was 1500000 Pa · s. The viscosity for 30 minutes after irradiation with ultraviolet rays was 157,000 Pa · s. The viscosity of the dam member is a value measured at 25 캜 and a shear rate of 2.5 (1 / s), as measured using a rheometer (trade name "Physica MCR301", manufactured by Anton Paar).

The UV delay curable damper was applied to the surface of glass (76 mm x 52 mm) using an auto dispenser to form a dam of 50 mm x 35 mm, and a filler (resin composition obtained in Example or Comparative Example) (15 to 50 mg) were dropped by 1 drop at a distance of not less than 1 mm, and slightly separated from the droplet so as not to contact each other.

(Irradiation amount: 1500 mJ / cm &lt; ² &gt;) at a point 10 cm away from the glass surface by using high pressure mercury of 200 W / cm or the like.

After 30 minutes, another piece of glass (76 mm x 52 mm) was placed on the glass surface, and the two glass pieces were sandwiched between the clips and bonded together in a vacuum chamber at a pressure of 2.5 torr. The bonded glass was heated at 100 占 폚 for 1 hour to obtain a glass test piece sealed by a dam and fill method. The boundary between the dam and the fill in the glass test piece was observed with a CCD camera and the leakage prevention property of the dam was evaluated according to the following criteria.

Evaluation standard

○: It was possible to prevent the peeling completely

△: A small amount of peel was spilled out

X: A large amount of the peel was spilled.

<Measurement of Refractive Index>

The refractive index of light at 589.3 nm was measured at 25 DEG C using a Model 2010 prism coupler (manufactured by Metricon) for the cured product (thickness: 100 mu m) obtained in Examples and Comparative Examples.

<Outgas amount>

The cured product (60 mg) obtained in the examples and the comparative examples was placed in a vial bottle, irradiated with ultraviolet rays (1500 mJ / cm ² ) and allowed to stand at 100 ° C for 1 hour, Respectively. Further, a calibration curve was prepared using toluene standard solution (toluene: 100 ppm as a standard substance, hexane: 60 mg as a solvent). HP-6890N (manufactured by Hewlett-Packard Company) was used as the measuring instrument, and DB-624 (manufactured by Agilent) was used as the column.

<Water vapor permeability>

(G / m ² · day · atm) of the cured product (thickness: 100 μm) obtained in Examples and Comparative Examples was measured at 60 ° C. and 90% RH in accordance with JIS L 1099 and JIS Z 0208 And the water vapor permeability was evaluated.

The compounds used in Examples and Comparative Examples are as follows.

[Compound (A)]

MPV: bis (4-vinylthiophenyl) sulfide, molecular weight: 302, trade name "MPV", manufactured by Sumitomo Seika Co.,

[Compound (B)]

VCZ: N-vinylcarbazole, molecular weight: 193.24, trade name "HRM-C01", manufactured by Nisshoku Techno Fine Chemical Co.,

ACZ: N-allylcarbazole, molecular weight: 207.16, manufactured by Nisshoku Techno Fine Chemical Co., Ltd.

OPP-EO-VE: (2-phenylphenoxy) ethyl vinyl ether obtained in Preparation Example 1, molecular weight: 240.16

HRD-01: 2- (o-phenylphenoxy) ethyl acrylate, molecular weight: 268, trade name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co.,

[Other curable compounds]

SY-OPG: o-phenylphenol glycidyl ether, trade name "SY-OPG", manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.

[Noncurable compound]

PVCZ: poly-N-vinylcarbazole, weight average molecular weight: 45000, SP value at 25 DEG C: 5.6, trade name "PVCZ", manufactured by Maruzen Sekiyu Kagaku Co.,

Neo Polymer 120: petroleum resin, weight average molecular weight: 1500, SP value at 25 占 폚: 11.2, trade name "Neopolymer 120", manufactured by JX Nikkoseki Energy Co.,

[Photo cationic polymerization initiator (C)]

Photo cationic polymerization initiator: 4- (4-biphenylylthio) phenyl-4-biphenylyl phenylsulfonium tetrakis (pentafluorophenyl) borate

The resin composition of the present invention is irradiated with ultraviolet rays and then bonded to a substrate provided with the organic EL device and heat treatment is performed after bonding to prevent the leakage from the dam, And can be sealed with a cured product having high refractive index, low moisture permeability and low outgassing property without directly exposing the organic EL element to ultraviolet rays.

Therefore, the resin composition of the present invention can be suitably used as a sealing agent of a top-emission type organic EL device, a light-emitting layer material of a bottom-emission type organic EL device, a solar cell material, a lens material and the like.

1: lead 2: dam
3: Dispenser 4: Resin composition
5: substrate 6: cathode
7: light emitting layer 8: anode

Claims (8)

A resin composition comprising the following compound (A), the following compound (B) and a cationic photopolymerization initiator (C).
Compound (A): A compound represented by the following formula (a)

(Wherein R ^a represents a reactive functional group, R ^b is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, A carboxyl group which may be protected by a protective group, a sulfo group which may be protected by a protecting group, a nitro group, a cyano group or an acyl group which may be protected by a protective group, R ^c represents a single bond or a linking group, m represents And n represents an integer of 0 to 10. The two R ^a may be the same or different from each other. A plurality of R ^b and m may be the same or different, being)
&Lt; / RTI &gt;
Compound (B): Compound (b-1) represented by the following formula

(Wherein Y represents a single bond or a linking group, and R ¹ represents a hydrogen atom or a methyl group)
&Lt; / RTI &gt; The resin composition according to claim 1, wherein R ^a in formula (a) is a vinyl group or allyl group. The positive resist composition according to claim 1 or 2, wherein the ratio of the content of the compound (A) to the content of the compound (B) (electron: latter ratio (weight ratio)) is 60:40 to 95: Is at least 50% by weight of the total amount of the curable compound contained in the resin composition. 3. The resin composition according to claim 1 or 2, wherein the viscosity at 25 DEG C is 10 mPa-s or more and less than 30 mPa-s. The resin composition according to claim 1 or 2, which is an organic electroluminescence element encapsulant. A method of manufacturing an organic electroluminescence device, characterized in that the organic electroluminescence device is sealed through the following steps 1 and 2.
Step 1: A coating film containing the resin composition according to claim 5 is irradiated with ultraviolet rays.
Step 2: A coating film after irradiated with ultraviolet rays obtained through Step 1 is adhered to the element mounting surface of the substrate provided with the organic electroluminescence element, and heat treatment is performed. An organic electro luminescence device having a configuration in which a device is sealed with a cured product of the resin composition according to claim 5. delete

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