KR20150090063A - Resin composition, and cured product(1) thereof - Google Patents

Abstract

An object of the present invention is to provide a cured product which is excellent in visible light transmittance and light fastness, has a high Tg, low water vapor transmission rate, a small viscosity (25 DEG C) of 1300 mPa.s or less and a liquid refractive index of 1.50 or more, Wherein the resin composition contains the following aromatic compound (A) and the following cyclic compound (B) and has a viscosity of not more than 1300 mPa 占 퐏 measured at 25 占 폚;
Aromatic compound (A): skeleton of biphenyl, bisphenol A, bisphenol F and bisphenol S represented by formula (AA) (abbreviated), alkylene having 1 to 4 carbon atoms represented by formula (AB) (A) having at least one skeleton selected from the group consisting of a phenylene skeleton, an anthracene skeleton and a phenanthrene skeleton which may be present and an oxetanyl group or an epoxy group,
Cyclic compound (B): cyclic compound (B) having an oxetanyl group or an epoxy group and satisfying the following conditions,
Conditions of the cyclic compound (B):
When the ring in the cyclic compound (B) is an aromatic ring, an aliphatic ring or a hetero ring, and among them, when the ring is an aromatic ring, the cyclic compound has a structure different from that of the compound used as the aromatic compound (A) (B) an aliphatic ring, the cyclic compound may be a compound having a cyclic hydrocarbon skeleton or cycloalkylene skeleton having a crosslinking structure and a cyclic compound having an oxetanyl group or an epoxy group Or an alicyclic epoxy resin.

Description

RESIN COMPOSITION AND CURED PRODUCT (1) {RESIN COMPOSITION, AND CURED PRODUCT (1) THEREOF}

Low moisture permeability materials are important materials in various industries. In particular, in the vicinity of electric and electronic devices and displays, a material which is indispensable for maintaining quality and which is required to have a higher performance and a low moisture permeability is required.

2. Description of the Related Art In recent years, displays have become widespread, with thin-type displays called flat panel displays (FPD), in particular plasma displays (PDP) and liquid crystal displays (LCD) In addition, an organic EL display (OLED) is expected as a next-generation self-emission type thin film display, and some commercial products have already been put to practical use. The organic EL element of the organic EL display has a structure in which an element body made of a thin film stacked body including a light emitting layer sandwiched between a cathode and an anode is formed on a substrate such as glass on which a driving circuit such as a TFT is formed. One layer of the light emitting layer or the electrode of the device section is likely to be deteriorated by moisture or oxygen, and deterioration in brightness, life, and discoloration occurs due to deterioration. For this reason, the organic EL element is sealed so as to block intrusion of moisture or impurities from the outside. In order to realize a high-quality and highly reliable organic EL device, a sealing material with higher performance is required, and various sealing techniques have been studied in the past.

As a typical sealing method of an organic EL device, a method of fixing a metal or glass sealing cap into which a desiccant has been inserted in advance is fixed to a substrate of an organic EL device using a sealing adhesive (Patent Document 1). In this method, an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is provided on the sealing cap, and then the adhesive is solidified to fix the substrate and the sealing cap, thereby sealing the organic EL element. In this method, the sealing by the glass sealing cap is the mainstream. However, since the glass sealing cap is manufactured by performing excavation processing for inserting a desiccant into a flat glass substrate, the glass sealing cap tends to be expensive. Further, since the sealing by the sealing cap inserts the desiccant into the inside of the sealing cap, light can not be drawn out from the sealing cap side. That is, the light emitted from the light source is drawn out from the substrate side of the element, and is limited to a bottom emission type element. In the case of a bottom-emission type device, there is a problem that the aperture ratio is reduced by the driving circuit portion formed on the substrate and the light is partially blocked by the driving circuit portion, thereby deteriorating the drawing efficiency. Therefore, it is required to develop a sealing method applicable to a top emission type device that draws light from the opposite side of the substrate of the organic EL device.

As typical sealing methods applicable to the top emission type device, there are a thin-film sealing method and a solid sealing method. In the thin-film sealing method, a thin film made of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2). In order to impart sufficient moisture-proofing property to the device by this method, it is necessary to sequentially laminate several thin films on the device. For this reason, the film-forming process is long in the thin-film sealing method, resulting in high cost, and there is a tendency that initial investment is increased by introduction of a large-sized vacuum gauge facility required for film formation.

On the other hand, the solid sealing method is a method in which a passivation film is formed so as to cover the entire element portion of the organic EL element, and a sealing transparent substrate is provided thereon through a sealing material. Generally, the passivation film is formed by vapor deposition or sputtering of an inorganic material, but it is often an incomplete film having a pinhole or a film having a weak mechanical strength. For this reason, in the solid sealing method, after forming a passivation film on a device, a transparent substrate for sealing such as a glass substrate is provided through a sealing adhesive to enhance the reliability of sealing. Further, a method of improving the reliability of sealing by filling the air gap with a thermosetting or photo-curable resin has also been studied. Such a solid sealing method has attracted attention as a method capable of sealing a top-emission-type device with ease and at a low cost.

In the sealing by the solid sealing method of the organic EL device, it is possible to use heat or photo-curing resin as the sealing adhesive or the surface sealing adhesive, but their characteristics are not likely to significantly affect the performance of the element and the productivity of the sealing operation Because it is very important. For example, if the water vapor transmission rate of the sealing adhesive is not sufficiently low, there is a possibility that the penetration into the element portion from the pinhole of the passivation film causes deterioration of the element. Further, if the curing reaction of the sealing material is slow, the curing process may take a long time and the productivity of the sealing operation may decrease.

The sealing adhesive used in these materials is required to have high transmittance in the visible light range, light resistance to withstand light emission, low moldability and shrinkability for suppressing stable formability and residual stress, low water vapor permeability for protecting the light emitting element from moisture, Is required. It is possible to perform sealing by a solid sealing method using a known adhesive as an adhesive for sealing an organic EL device. However, it is difficult to obtain a result that can satisfy both reliability and productivity, It is required to develop a sealing adhesive which can be preferably used for the sealing adhesive.

Japanese Patent No. 4876609 Japanese Patent Laid-Open Publication No. 2012-059553 Japanese Patent No. 4655172 Japanese Patent Application Laid-Open No. 2001-81182 Japanese Patent Application Laid-Open No. 2011-225773 Japanese Patent No. 4850231

An object of the present invention is to provide a cured product of a sealing material for an organic EL device, particularly a resin composition suitable for surface sealing, a cured product excellent in visible light transmittance, light resistance and curability, high in Tg and low in shrinkage shrinkage and vapor permeability.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition having a specific composition and having a viscosity of a certain value or less and a cured product thereof solve the above problems and completed the present invention.

That is, the present invention relates to the invention described in the following (1) to (25).

(1) at least one skeleton selected from the group consisting of a skeleton represented by formula (AA) below, a skeleton represented by formula (AB) below, an anthracene skeleton and a phenanthrene skeleton, (B) having an oxetanyl group or an epoxy group and satisfying the following condition (iii) and having a viscosity measured at 25 占 폚 of 1300 mPa 占 퐏 By weight or less of the total weight of the composition.

(i) a skeleton represented by the formula (A-A)

(Wherein X represents a direct bond, a sulfur atom or a dimethylmethylene group, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 4)

(ii) a skeleton represented by the formula (A-B)

(Wherein R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4)

(iii) Conditions of cyclic compound (B):

When the ring in the cyclic compound (B) is an aromatic ring, an aliphatic ring or a hetero ring, and among them, when the ring is an aromatic ring, the cyclic compound has a structure different from that of the compound used as the aromatic compound (A) (B) an aliphatic ring, the cyclic compound is an alicyclic hydrocarbon skeleton or cycloalkylene skeleton having a crosslinked structure, and a cyclic compound or alicyclic epoxy resin having an oxetanyl group or an epoxy group.

(2) The resin composition according to (1), wherein the aromatic compound (A) has a skeleton selected from the group described in the following (A-1).

A-1: phenyl, biphenyl, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S

(3) The resin composition according to the above (1) or (2), wherein the aromatic compound (A) is a compound having a skeleton selected from the group consisting of phenyl, biphenyl and bisphenol A as an aromatic skeleton.

(4) The resin composition according to any one of (1) to (3), wherein the cyclic compound (B) has a ring selected from the group described in the following (B-1).

B-1: an aromatic ring, the aliphatic ring and the heterocycle

(5) The resin composition according to (1), wherein the cycloalkylene skeleton forms a skeleton represented by the following formula (B-A).

(Wherein Y represents a direct bond, a sulfur atom or a methylene group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and t represents an integer of 1 to 4)

(6) The resin composition according to the above (1), wherein the cyclic compound (B) is an alicyclic epoxy resin.

(7) The resin composition according to any one of (1) to (4) above, wherein the ring of the cyclic compound (B) is an aromatic ring.

(8) The resin composition according to (7), wherein the cyclic compound (B) has a skeleton selected from the group described in the following (B-2)

B-2: phenyl, biphenyl, naphthalene, binaphthalene, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S.

(9) The resin composition according to (8), wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of phenyl, biphenyl, naphthalene, binaphthalene and bisphenol A.

(10) The resin composition according to any one of (1) to (4), wherein the cyclic compound (B) has a skeleton selected from the group described in the following (B-3).

B-3: Isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S.

(11) The resin composition according to (4) or (10), wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of adamantane, cyclohexane and hydrogenated bisphenol A.

(12) The resin composition according to any one of (1) to (4), wherein the cyclic compound (B) has a skeleton selected from the group described in the following (B-4).

B-4: Morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine.

(13) The resin composition according to (4) or (12), wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of oxane, dioxane and triazine.

(14) The resin composition according to any one of (1) to (13), further containing a curing agent (C).

(15) The resin composition according to (14), wherein the curing agent (C) is a photo cationic polymerization initiator.

(16) The resin composition according to the above (15), wherein the photo cationic polymerization initiator is at least one selected from the group described in the following (C-1).

C-1: sulfonium salts, iodonium salts, phosphonium salts, ammonium salts and antimonates

(17) The resin composition according to (14), wherein the curing agent (C) is a heat curing agent.

(18) The resin composition according to (17), wherein the thermosetting agent is selected from the group described in (C-2) below.

C-2: amine compound, acid anhydride compound, amide compound, phenol compound, carboxylic acid compound, imidazole compound, isocyanuric acid adduct, metal compound, sulfonium salt, ammonium salt, antimonate, Phonium salt, microcapsule type curing agent.

(19) The resin composition according to any one of (1) to (18) above, which contains 20 to 80 parts by mass of the aromatic compound (A) per 100 parts by mass of the total amount of the aromatic compound (A) Composition.

(20) A process for producing a toner according to any one of (1) to (19), wherein the cyclic compound (B) is contained in an amount of 20 to 80 parts by mass per 100 parts by mass of the total amount of the aromatic compound (A) Resin composition.

(21) The resin composition as described in any one of (1) to (20) above, which contains 0.1 to 5 parts by mass of a curing agent (C) when the total amount of the aromatic compound (A) and the cyclic compound (B) Composition.

(22) A cured product having a thickness of 100 탆 and having a water vapor transmission rate of 35 g / m ² ∙ 24 hr or less as measured at 60 캜 and a relative humidity of 90% Composition.

(23) An organic EL display in which the resin composition according to any one of (1) to (22) above is cured to obtain a cured product.

(24) A film for surface sealing of an organic EL display having a barrier performance obtained by applying the resin composition according to any one of (1) to (22) above to a substrate and curing.

(25) Use of the resin composition according to any one of (1) to (22) for surface sealing of an organic EL device.

(Effects of the Invention)

The resin composition of the present invention has a low viscosity, and the cured product has excellent visible light transmittance and light resistance, has a high Tg, and has a low shrinkage percentage and water vapor permeability. Particularly, Suitable.

Examples of the aromatic compound (A) contained in the resin composition of the present invention include oxetane compounds or epoxy compounds exemplified below.

The aromatic compound (A) contained in the resin composition of the present invention has at least one skeleton selected from the group consisting of a skeleton represented by the formula (AA), a skeleton represented by the formula (AB), an anthracene skeleton and a phenanthrene skeleton And an aromatic compound (A) further having an oxetanyl group or an epoxy group.

In the present invention, the anthracene skeleton or the phenanthrene skeleton may or may not have a substituent. As the substituent, the alkyl group, alkoxy group or alkenyl group may be mentioned, and these groups are all preferably 1 to 4 carbon atoms.

In the present invention, as the aromatic compound (A), the following formula (A-A)

(Wherein X represents a direct bond, a sulfur atom or a dimethylmethylene group, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 4) or a skeleton represented by the following formula AB)

(Wherein R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4, provided that the skeleton represented by the formula (AA) is excluded) A skeleton selected from the group consisting of an anthracene skeleton and a phenanthrene skeleton, and an aromatic compound having an oxetanyl group or an epoxy group are used.

By combining the aromatic compound (A) (hereinafter also referred to as component (A)) with the cyclic compound (B) (hereinafter also referred to as component (B)), an excellent moisture resistance effect can be obtained. The above skeleton becomes a sufficient barrier against moisture and suppresses moisture permeation.

In the formula (A-A) skeleton, it is particularly preferable that X is a direct bond or a dimethylmethylene group and is directly bonded (biphenyl skeleton).

It is preferable that the (A-A) skeleton, the (A-B) skeleton, the anthracene skeleton or the phenanthrene skeleton and the oxetanyl group or the epoxy group are connected directly or by a hydrocarbon group.

When an oxetanyl group or an epoxy group is connected to the skeleton by a hydrocarbon group, the hydrocarbon group includes an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms having an ether bond. The ether bond may be either in the above alkylene group or at the terminal of any of the alkylene groups. Preferably an alkylene group having 1 to 4 carbon atoms (more preferably an alkylene group having 1 to 3 carbon atoms), an alkylene-oxygen atom having 1 to 4 carbon atoms, an alkylene group having 1 to 4 carbon atoms (more preferably an alkylene group having 1 to 4 carbon atoms, An alkylene group having 2 to 10 carbon atoms (more preferably 2 to 6 alkylene groups) containing an ether bond between carbon atoms such as an alkylene group having 1 to 3 alkylene-oxygen atoms and an alkylene group having 1 to 3 carbon atoms, , An alkyl group having 1 to 4 carbon atoms (an alkyl group having 1 to 4 oxy-carbon atoms, more preferably an alkyl group having 1 to 4 oxy-carbon atoms) having an ether bond at the terminal of the alkylene group. When an ether bond is present at the terminal, an ether group is usually bonded to an aromatic ring and an alkyl group is bonded to an oxetane ring or an epoxy ring.

Examples of the aromatic compound (A) containing an oxetanyl group include oxetane compounds exemplified below.

For example, there can be mentioned 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,2-bis [ Methoxy] benzene, 4,4'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [ 3,3'-tetramethyl [4,4'-bis (3-ethyloxetan-3-yl) methoxy] biphenyl, 2, Oxetane such as 7-bis [(3-ethyloxetan-3-yl) methoxy] naphthalene and 4,4'-bis [(1-ethyl-3-oxetanyl) methyl] thiodibenzene thioether acid Compounds.

Examples of the aromatic compound (A) having an epoxy group include epoxy compounds having a phenyl skeleton such as styrene oxide and phenyl glycidyl ether, biphenyl glycidyl ether, biphenyl diglycidyl ether, p-tert-butylphenylglycidyl Ether, 3,3 ', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, phenylaralkyl type epoxy compounds and biphenyl aralkyl type epoxy compounds Bisphenol A diglycidyl ether such as bisphenol A diglycidyl ether or brominated bisphenol A diglycidyl ether, such as epoxy compounds having a biphenyl skeleton, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds and the like, Bisphenol S type epoxy compounds such as epoxy compounds, bisphenol S diglycidyl ether or brominated bisphenol S diglycidyl ether, bisphenyl fluorene diglycidyl ether or bisphenyl fluorene ethanol glycidyl ether Of the fluorene-skeleton epoxy compound having a (preferably bisphenyl fluorene skeleton) and the like are listed.

Examples of the biphenyl aralkyl epoxide compound include those of the following formula (A-Aa).

The formula (A-Aa)

(Wherein G represents a glycidyl group and p represents an integer of 1 to 50)

As the compound of the above formula (A-Aa), commercially available o-phenyl phenol glycidyl ether (product of SANKO CO., LTD.) And the like can be mentioned.

Specific skeletons of the component (A) include skeletons selected from the group described in the following (A-1).

A-1: phenyl, biphenyl, naphthalene, binaphthalene, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S

Among the above skeletons of the component (A), the phenyl skeleton (excluding the skeleton of the formula (A-A), the same shall apply hereinafter), the biphenyl skeleton, the bisphenol A skeleton or the bisphenol S skeleton are preferable in the resin composition of the present invention. More preferably a biphenyl skeleton and a bisphenol A skeleton having a low viscosity, a low moisture permeability, and a high light transmittance. Above all, a biphenyl skeleton is more preferable.

The component (A) is preferably the component (A) having one oxetanyl group or epoxy group, more preferably the skeleton is the above-mentioned preferable skeleton or more preferable skeleton. More preferably a biphenyl skeleton-containing monoepoxy compound or a monooxetanyl compound.

The component (A) may have either an oxetanyl group or an epoxy group, but an epoxy group is more preferable.

Examples of the more preferable aromatic compound (A) having an epoxy group include a biphenyl skeleton-containing monoepoxy compound, a phenyl skeleton-containing monoepoxy compound such as phenylphenol glycidyl ether (more preferably, o-phenylphenol glycidyl ether) or Limonene oxide.

The content of the component (A) of the present invention is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, based on 100 parts by mass of the total of the component (A) + the component (B) which is a reactive compound. In order to achieve low moisture permeability, the functional group equivalent of the component (A) is preferably 10 to 500 g / eq, more preferably 50 to 250 g / eq.

As the cyclic compound (B) contained in the resin composition of the present invention, an oxetane compound or an epoxy compound having an aromatic ring having a specific skeleton, an oxetane compound or an epoxy compound having an aliphatic ring having a specific skeleton, oxetane Compounds or epoxy compounds.

The ring in the cyclic compound (B) includes a ring selected from the group described in the following (B-1).

B-1: aromatic ring, aliphatic ring and heterocyclic ring

Here, when an oxetane compound or an epoxy compound having an aromatic ring is selected as the cyclic compound (B), a compound having a structure different from the structure of the compound selected as the aromatic compound (A) is used.

The cyclic compound (B) is preferably a cyclic compound (B) having a plurality of (at least two) oxetanyl groups or epoxy groups.

Examples of the oxetane compound or epoxy compound having an aromatic ring which can be used as the cyclic compound (B) include the same compounds as those exemplified as the aromatic compound (A). In the present invention, , It is important to use a compound having a different structure from the compound used as the aromatic compound (A) as the cyclic compound (B), as described above.

Specific examples of the aromatic ring skeleton in the cyclic compound (B) having an aromatic ring include a skeleton selected from the group described in the following (B-2).

B-2: phenyl, biphenyl, naphthalene, binaphthalene, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S

Among these, preferred skeletons are skeletons selected from the group consisting of phenyl, biphenyl, naphthalene, binaphthalene and bisphenol A.

Specific compounds are listed below.

Examples of the oxetane compound having an aromatic ring which can be used as the cyclic compound (B) include the same ones listed in the component (A), and specific examples thereof include the following compounds.

For example, there can be mentioned 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,2-bis [ Methoxy] benzene, 4,4'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [ 3,3'-tetramethyl [4,4'-bis (3-ethyloxetan-3-yl) methoxy] biphenyl, 2, Methoxy] naphthalene, 4,4'-bis [(1-ethyl-3-oxetanyl) methyl] thiodibenzene thioether acid and the like are listed .

As the epoxy compound having an aromatic ring which can be used as the cyclic compound (B), the following compounds can be exemplified.

Examples thereof include epoxy compounds having a phenyl skeleton such as styrene oxide and phenyl glycidyl ether, biphenyl glycidyl ether, biphenyl diglycidyl ether, p-tert-butylphenyl glycidyl ether, 3,3 Epoxy compounds having a biphenyl skeleton such as 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl and biphenyl aralkyl type epoxy compounds, Bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, Bisphenol S type epoxy compounds such as bisphenol S diglycidyl ether, bisphenyl fluorene diglycidyl ether, and bisphenyl fluorene ethanol diglycidyl ether; epoxy compounds having a fluorene backbone such as glycidyloxy Naphthalene, 1,6- Epoxy compounds having a naphthalene skeleton such as bis (2,3-epoxypropane-1-yloxy) naphthalene, non-naphthalene glycidyl ether, non-naphthalene diglycidyl ether and binaphthol ethanol diglycidyl ether. .

In the present invention, when an oxetane compound or an epoxy compound having an aromatic ring is selected as the cyclic compound (B), an aromatic ring having a structure different from the compound selected as the component (A) and an oxetanyl group or an epoxy group Is used. In that case, the resin composition of the present invention contains an oxetane compound or an epoxy compound having two other kinds of aromatic rings.

When a compound having an aromatic ring is selected as the cyclic compound (B), preferable examples of the skeleton containing the aromatic ring include a phenyl skeleton, a biphenyl skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton or a naphthalene skeleton have. More preferably a biphenyl skeleton, a bisphenol A skeleton or a naphthalene skeleton having a low viscosity, a low moisture permeability and a high light transmittance. More preferably a biphenyl skeleton or a bisphenol A skeleton, and most preferably a bisphenol A skeleton. The viscosity of these compounds is preferably 1500 mPa 占 퐏 or less.

As the preferable cyclic compound (B) having an aromatic ring, cyclic compound (B) having the above preferable skeleton can be mentioned, and cyclic compound (B) having more preferable skeleton, more preferable skeleton and most preferable skeleton is more preferable The cyclic compound (B), the more preferable cyclic compound (B), and the most preferable cyclic compound (B). In the cyclic compound (B), any of an oxetanyl group and an epoxy group may be used, and an epoxy group is usually preferable. Particularly, as the cyclic compound (B), an epoxy compound having a biphenyl skeleton or a bisphenol A skeleton is preferable, and a compound having a plurality of epoxy groups is particularly preferable.

The content of the component (B) of the present invention is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, based on 100 parts by mass of the total amount of the component (A) + the component (B) To achieve low moisture permeability, the functional group equivalent of the component (B) is preferably 10 to 1000 g / eq, more preferably 50 to 500 g / eq.

In addition, from the viewpoint of low moisture permeability, other compounds are used as the component (A) and the component (B). This is considered to be effective for a compound having a high electron density to lower the moisture permeability, but it is important not only the electron density but also the balance with the cross-linking density between the compounds. Therefore, in order to lower the moisture permeability, for example, a compound having a phenyl skeleton, a biphenyl skeleton or a bisphenol A skeleton and having one polymerizable group (oxetanyl group or epoxy group) is used as the component (A) As the component (B), a compound having a phenyl skeleton, a biphenyl skeleton, a bisphenol A skeleton, or a naphthalene skeleton and having a plurality of (two to three or more) polymerizable groups (oxetanyl or epoxy groups) to be. As an example of a more preferable combination, a compound having a biphenyl skeleton or a bisphenol A skeleton and having one oxetanyl group or epoxy group (preferably a compound having one epoxy group) is used as the component (A) A compound having a phenyl skeleton, a biphenyl skeleton or a bisphenol A skeleton and having a plurality (at least two) of an oxetanyl group or an epoxy group (preferably an epoxy group) or a cyclohexane skeleton-containing epoxy compound (for example, Oxide, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and hydrogenated bisphenol diglycidyl ether compound). The hydrogenated bisphenol diglycidyl ether compounds include hydrogenated bisphenol A, F or S diglycidyl ethers. All of the compounds used as the component (A) and the component (B) preferably have a viscosity of 1300 mPa · s or less, more preferably 800 mPa · s or less, and furthermore preferably 500 mPa · s or less.

Next, the cyclic compound (B) having an aliphatic ring in the cyclic compound (B) will be described in detail below.

In the present invention, as the cyclic compound (B) having an aliphatic ring, a cyclic compound having an alicyclic hydrocarbon skeleton or cycloalkylene skeleton having a cross-linking structure and a cyclic compound having an oxetanyl group or an epoxy group or an alicyclic epoxy resin is used.

The alicyclic hydrocarbon skeleton or cycloalkylene skeleton (a cycloalkylene skeleton having no cross-linking structure) having a cross-linking structure described above may or may not have a substituent. The substituent in the case of having a substituent includes an alkyl group, an alkenyl group and an alkoxy group, and these groups preferably have 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

As the aliphatic ring skeleton in the cyclic compound (B) having an aliphatic ring, an alicyclic hydrocarbon skeleton having a cross-linking structure (preferably an alicyclic hydrocarbon skeleton having a cross-linking structure of 7 to 10 carbon atoms) and a cross-linking structure (Preferably a cycloalkylene skeleton having 4 to 7 carbon atoms, more preferably a cycloalkylene skeleton having 5 or 6 carbon atoms, more preferably a cyclohexyl skeleton). In the cycloalkylene skeleton, the cyclohexylene skeleton may be a skeleton represented by the following formula (B-A), wherein two cyclohexylene skeletons are bonded through a direct bond or a linking group.

(Wherein Y represents a direct bond, a sulfur atom or a methylene group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and t represents an integer of 1 to 4)

The cycloaliphatic skeleton of the cyclic compound (B) is preferably a cycloalkylene skeleton having 4 to 7 carbon atoms and no cross-linking structure, more preferably a cycloalkylene skeleton having 5 or 6 carbon atoms , And most preferably a divalent cyclohexylene skeleton. In addition, the cyclohexylene skeleton may form a skeleton represented by the formula (B-A).

Examples of the alicyclic skeleton in the cyclic compound (B) include skeletons selected from the group described in the following B-3, more preferably cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and Hydrogenated bisphenol S.

B-3: Isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S

Of the cycloalkylene skeletons which do not contain a crosslinked structure, a cyclohexylene skeleton is most preferable. In the case of a cyclohexylene skeleton, a cyclohexane skeleton which does not form a skeleton represented by the formula (BA) is preferred, or a skeleton represented by the formula (BA) is preferably formed, so that the cyclohexylene skeleton can be suitably selected and used .

As the cyclic compound (B) having an aliphatic ring to be used in the present invention, a cyclic compound having an aliphatic cyclic skeleton and an oxetanyl group or an epoxy group or an alicyclic epoxy resin can be mentioned.

By combining the cyclic compound (B) with the aromatic compound (A), an excellent moisture resistance effect can be obtained. The above skeleton becomes a sufficient barrier against moisture and suppresses moisture permeation.

In the formula (B-A) skeleton, Y is preferably a direct bond or a methylene group, and particularly preferably a direct bond.

The alicyclic hydrocarbon skeleton having a crosslinked structure is specifically exemplified by adamantane skeleton, dicyclopentadiene skeleton and isobornyl skeleton, and in some cases, an adamantane skeleton or an isobornyl skeleton is preferable Do.

Specific examples of the cycloalkylene skeleton (cycloalkylene skeleton having no cross-linking structure) include cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, and the like. As described above, (BA) skeleton may be formed by bonding through a linking group.

The alicyclic hydrocarbon skeleton having a crosslinking structure, the cycloalkylene skeleton (including the above (BA) skeleton), and the oxetanyl or epoxy group may be bonded directly or via a hydrocarbon group (which may contain an ether bond) desirable.

As a specific linkage, an oxetanyl group or an epoxy group is bonded to a hydrocarbon group, and the hydrocarbon group is directly or ether-bonded to an aliphatic ring. When the hydrocarbon group is bonded by a hydrocarbon group, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms having an ether bond are listed. As the hydrocarbon group containing an ether bond as a preferable linking group, an alkylene-oxygen atom having 1 to 4 carbon atoms, an alkylene group having 1 to 4 carbon atoms (more preferably an alkylene-oxygen atom having 1 to 3 carbon atoms, An alkylene group having 2 to 10 carbon atoms (more preferably 2 to 6 alkylene groups) containing an ether bond between the carbon atoms or an ether bond such as an oxymethyl group at the terminal of the alkylene group -4 alkylene groups (alkyl groups having 1 to 4 carbon atoms) (more preferably, alkyl groups having 1 to 3 oxy-carbon atoms), and the like. When the alkylene group has an ether bond at the terminal thereof, usually an ether group is bonded to an aliphatic ring and an alkyl group is bonded to an oxetane ring or an epoxy ring. In addition, an epoxy group may be directly formed in an aliphatic ring such as an alicyclic epoxy resin.

Examples of the oxetane compound having such an aliphatic ring include 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5.2.1.2.6] do.

Examples of such an epoxy compound having an aliphatic ring include aliphatic epoxy compounds such as limonene oxide, the alicyclic epoxy resins described in the following formulas (b-1a), (b-1b) and (b-1c), hydrogenated bisphenol A epoxy compounds, Bisphenol F type epoxy compounds such as glycidyl ether and brominated hydrogenated bisphenol F diglycidyl ether, bisphenol S type epoxy compounds such as hydrogenated bisphenol S diglycidyl ether and hydrogenated bisphenol S diglycidyl ether, An epoxy compound having a tricyclodecane skeleton such as tricyclodecane and tricyclodecane diglycidyl ether, and an epoxy compound having an adamantane skeleton such as adamantane glycidyl ether.

Formula (b-1a):

The formula (b-1b)

The formula (b-1c)

(n is an average value of 1 to 5)

As the compound having an aliphatic ring in the cyclic compound (B), a cyclic compound (B) having a skeleton selected from the group consisting of an alicyclic epoxy resin or an isobornyl skeleton, an adamantane skeleton and a hydrogenated bisphenol A skeleton is preferable . Particularly, a cyclic compound (B) having an alicyclic epoxy resin or an adamantane skeleton is preferable in view of colorlessness, excellent reactivity and high glass transition point.

The content of the cyclic compound (B) having an aliphatic ring of the present invention is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, per 100 parts by mass of the total amount of the component (A) + component (B) to be. In order to achieve low moisture permeability, the functional group equivalent of the cyclic compound (B) is preferably 10 to 1000 g / eq, more preferably 50 to 500 g / eq.

Examples of the heterocycle include a morpholine skeleton, a tetrahydrofuran skeleton, an oxane skeleton, a dioxane skeleton, a triazine skeleton, a carbazole skeleton, a pyrrolidine skeleton, and a piperidine skeleton. These may have a substituent or may not have a substituent. When the substituent has a substituent, examples of the substituent include an alkyl group, an alkoxy group and an alkenyl group, and usually have about 1 to 4 carbon atoms.

The heterocyclic skeleton and the oxetanyl group or the epoxy group may be bonded directly or may be connected by a divalent hydrocarbon group, but are connected by a common divalent hydrocarbon group. When the hydrocarbon group is bonded by a hydrocarbon group, an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms having an ether bond are listed.

Examples of the oxetane compound having a heterocycle include reaction products of isocyanuric acid (CIC acid) and oxetane alcohol.

Examples of the epoxy compound having a heterocyclic ring include compounds having an isocyanurate skeleton such as 1,3,5-triglycidylisocyanurate and compounds having a dioxane glycol skeleton such as dioxane glycol diglycidyl ether Epoxy compounds.

As the component (B) having a heterocycle, a compound having an isocyanurate skeleton is preferable, and a reaction product of a CIC acid and an oxetane alcohol, 1,3,5-triglycidylisocyanurate is particularly preferable.

The content of the component (B) having a heterocycle is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, based on 100 parts by mass of the total amount of the component (A) + the component (B) The functional group equivalent of the above-mentioned component (B) is preferably 10 to 500 g / eq, more preferably 50 to 250 g / eq, in order to improve the moisture permeability.

The present invention is a curable resin composition containing the above-mentioned component (A) and the aforementioned component (B), and a preferable combination as a combination of these components will be described below.

As a preferable combination, any one of the above-mentioned component (A) or the above-mentioned component (B) is preferably a curable resin composition having a weight average molecular weight of 2000 or less, more preferably 1000 or less, particularly preferably 500 or less. By using such a low-molecular-weight compound in any one of the component (A) and the component (B), it is possible to obtain a composition excellent in the production of an OLED by spreading after coating at a low point while securing low hygroscopicity.

Further, in the case of thermal curing, it is also preferable to use any one of the component (A) and the component (B) as an oxetane compound. This is because a resin composition having excellent curability in a short time can be obtained while ensuring low hygroscopicity by using any one of them as an oxetane compound.

The ratio of (A) / (B) is preferably 8/2 to 2/8, and more preferably 7/3 to 3/7 as the ratio of the component (A) to the component (B).

In the case where it is desired to improve the Tg (glass transition point), the bisphenol A skeleton may be introduced into the aromatic compound, and the dicyclopentadiene skeleton, the isobornyl skeleton and the adamantane skeleton may be introduced in the case of the alicyclic compound.

In particular, in the present invention, since the viscosity of the resin composition (viscosity measured at 25 캜: the same shall apply hereinafter) is usually not more than 1,500 mPa s, preferably not more than 1,300 mPa s, more preferably not more than 1,200 mPa,, ) And the component (B) are mixed, it is preferable that the viscosity is not more than the above-mentioned viscosity.

In the present invention, as the component (A), a monofunctional aromatic compound having a biphenyl skeleton and an oxetanyl group or an epoxy group, preferably a biphenyl skeleton-containing epoxy compound having one epoxy group (preferably, Biphenyl skeleton-containing monoglycidyl ether), more preferably o-phenylphenol glycidyl ether, and as the component (B), a multifunctional cyclic compound having at least two oxetanyl groups or epoxy groups (B ) Is preferably used. As the polyfunctional cyclic compound (B), a cyclic compound having an aromatic ring or an alicyclic ring which is not crosslinked, considering the viscosity of the resin composition, the low water vapor permeability of the cured product, the low hardening shrinkage ratio, (B) is preferable. The polyfunctional cyclic compound (B) preferably has a viscosity of 1400 mPa · s or less, preferably 1350 mPa · s or less and an aromatic ring skeleton having 5 to 7 carbon atoms having no skeleton or bridging represented by the formula (AA) Cyclic compound (B) having a cycloalkane skeleton and the like are preferable. More preferably an epoxy compound having a viscosity of 1400 mPa s or less, preferably 1350 mPa s or less and having a skeleton represented by the formula (AA) as the aromatic ring skeleton and having at least two epoxy groups and / More preferably a polyglycidyl ether compound having a viscosity of 1350 mPa 占 퐏 or less and having a biphenyl skeleton or a bisphenol A skeleton and / or 3,4-epoxycyclohexenylmethyl -3 ', 4'-epoxycyclohexene carboxylate.

In some cases, an oxetane compound or an epoxy compound having a condensed ring structure such as fluorene or carbazole may also be used as the cyclic compound (B).

The alicyclic epoxy resin as the component (B) is preferable because of its low viscosity and good processability and excellent curing speed. Among the alicyclic epoxy compounds, aliphatic epoxies are preferably bifunctional, and 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate is particularly preferable.

Further, an oxetane compound or an epoxy compound having a condensed ring structure such as fluorene or carbazole other than the component (A) and the component (B) can also be used as needed, and the coating film can be given rigidity. These oxetane compounds or epoxy compounds may be used alone or in combination of two or more.

The curing agent (C) contained in the resin composition of the present invention is reactive with the components (A) and / or (B). As the curing agent, a compound which causes a curing reaction with an energy ray such as light or heat can be used. In the present invention, any of them can be used, but usually a curing agent (C) which causes a curing reaction with an energy ray is preferable.

As the curing agent (C) which causes a curing reaction with an energy ray such as light, any compound capable of generating a cation by receiving ultraviolet rays (wavelengths of about 200 to 400 nm) can be used without limitation, and, for example, a cationic polymerization initiator, And sulfonium salts, iodonium salts, phosphonium salts, ammonium salts and antimonates are exemplified.

Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis [diphenylsulfonio] Diphenylsulfide-bishexafluoroantimonate, 7-di ((? - hydroxyethoxy) phenylsulfonyl] diphenylsulfide-bishexafluoroantimonate, diphenylsulfide-bishexafluorophosphate, p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate , 7-di (p-toluyl) sulfonio] -2-isopropyltetrakis (pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfo-diphenylsulfide-hexafluoro Phenylphosphonium-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphe 4-tert-butylphenylcarbonyl-4'-diphenylsulfone-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'- Diphenylsulfone-diphenylsulfide-tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, a halide of thiophenyldiphenylsulfonium hexafluoroantimonate, a 4,4 ', 4' Bis (diphenylsulfanyl) diphenylsulfide-bishexafluoroantimonate, diphenyl [diphenylsulfone] diphenylsulfide-bis (hexafluoroethoxyphenyl) sulfonium hexafluoroantimonate, 4,4'- 4- (phenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tri [(Trifluoromethyl) sulfonyl] and the like bumetanide.

Examples of the iodonium salt include diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate , (Tricumyl) iodonium tetrakis (pentafluorophenyl) borate, and the like.

Examples of the phosphonium salt include tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyl tributylphosphonium chloride and the like.

Examples of the ammonium salt include benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide.

Examples of the antimonates include triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4 - (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate and diaryl iodonium hexafluoroantimonate, and the like.

As the curing agent (C) (photo cationic polymerization initiator) which causes curing reaction with energy rays such as light used in the present invention, iodonium salts and sulfonium salts are preferable, and among them, those having high sensitivity and being easily available from the market (4-fluorophenyl) borate, thiophenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (pentafluorophenyl) (Phenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [ Trifluoromethyl) sulfonyl] methanide and the like are preferable.

Considering the environmental and human health hazards and regulations of various countries, it is preferable to use iodonium tetrakis (pentafluorophenyl) borate not containing antimony element (tricumyl), diphenyl [4- (phenylthio) phenyl] (Trifluoromethyl) sulfonyl] methanide is most preferably used in the present invention, and it is most preferable to use tetra [4- (4-acetylphenylsulfanyl) phenyl] sulfoniumtris [(trifluoromethyl) sulfonyl]

The content of the photo cationic polymerization initiator of the present invention is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the component (A) + the component (B). In the resin composition of the present invention, the cationic photopolymerization initiator may be used singly or in combination of plural kinds thereof.

Examples of the heat curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include a polyamide resin synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylene diamine , Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclo Hexane-1,3,4-tricarboxylic acid-3,4-anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'- Phenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol Tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, naphthalene diol, Alkyl substituted naphthols, dihydroxybenzenes, dihydroxynaphthalenes, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o- Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 '-Bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, and the like, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane- Amine complexes, guanidine derivatives, condensates of terpenes and phenols, and the like, but are not limited thereto. These may be used alone, or two or more kinds may be used.

In many cases, it is preferable to use acid anhydrides which are excellent in transparency after curing for sealing materials in sealing materials, particularly in organic EL. In particular, it is preferable to use acid anhydrides such as methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride , Methylhexahydrophthalic anhydride, butane tetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3 -Dicarboxylic acid anhydride, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. As the acid anhydride having an alicyclic skeleton, a commercially available product can be used. For example, as an H-TMA series in Mitsubishi Gas Chemical Company, Inc. or the like, a solid product or a liquid product (although it is a liquid product, Semi-solid state, and workability is extremely poor).

In the case of using cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, the use of the cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride may result in poor workability because it is a solid or a semi-solid state with high viscosity. Therefore, it is preferable to use it in combination with another curing agent, preferably an acid anhydride having an alicyclic skeleton. The curing agent which can be used in this case is not particularly limited as long as it is in the form of a liquid and has a low viscosity. For example, HNA-100 (New Japan Chemical Co., Ltd.) containing anhydrous methylnadic acid and anhydrous nadic acid is used as a commercially available curing agent. , LTD.), or a ricaside MH700 (manufactured by New Japan Chemical Co., Ltd.) containing hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. When used in combination, a solid or semi-solid cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and a curing agent having a low viscosity are preliminarily cured at room temperature or under heating (preferably, Is 150 DEG C or less, and more preferably 120 DEG C) until it becomes uniform. Further, from the viewpoints of handling workability and exfoliation of the sealing material after curing, the use ratio of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in the total curing agent is preferably 20 to 90% And more preferably 30 to 80 mass% or less. When the mixing ratio exceeds 90% by weight, the workability as an extreme hardening agent is poor. If the content is less than 20% by mass, there is a fear that the improvement effect is diminished in view of the exfoliation of the sealing material.

The compounding ratio of the system using the heat curing agent of the present invention is determined by the equivalent of the functional group contained in the epoxy compound or the oxetane compound and the equivalence of the carboxyl group of the carboxylic acid curing agent. Preferably, the carboxyl group is preferably 0.2 to 5 equivalents, more preferably 0.5 to 2 equivalents, based on 1 equivalent of the functional group. When the amount exceeds the above range, the curing reaction does not sufficiently proceed, and excessive functional groups and residual carboxyl groups are produced, so that the toughness and heat resistance of the cured product can not be sufficiently exhibited.

In the resin composition of the present invention, a curing catalyst may be used alone or in combination with a curing catalyst without using a curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl- Benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) (2 '-ethyl, 4-methylimidazole (1')) ethyl-s-triazine, 2-ethyl- , 4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole 2: 3 adduct of isocyanuric acid , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, Diethyl-2-phenyl-3,5-dicyaethoxymethylimidazole, various imidazoles Salts thereof with polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid; amides such as dicyandiamide; -Diaza-bicyclo (5.4.0) undecene-7, and salts thereof such as tetraphenylborate and phenol novolac, salts with polycarboxylic acids or phosphinic acids, tetrabutylammonium bromide , Ammonium salt-based thermal cation initiators such as cetyltrimethylammonium bromide and trioctylmethylammonium bromide, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphoniumtetraphenylborate and the like Ruthenium phosphonium compound-based thermal cationic initiator, 1-naphthylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate, benzylmethyl-p-hydroxyphenylsulfone Antimonate-based thermal cationic initiators such as hexafluoroantimonate, dimethyl-p-acetoxyphenylsulfonium hexafluoroantimonate, and 1-naphthylmethyl-p-hydroxyphenylsulfonium hexafluorophosphate , Benzylmethyl-p-hydroxyphenylsulfonium hexafluorophosphate, dimethyl-p-acetoxyphenylsulfonium hexafluorophosphate, and other phosphonium salt-based thermal cation initiators such as 2,4,6-trisaminomethylphenol and the like Metal compounds such as phenols, amine adducts and tin octylate, and microcapsule type curing accelerators containing these curing accelerators as microcapsules. Which of these curing accelerators are used is appropriately selected depending on, for example, transparency, curing rate, and characteristics required for a transparent resin composition obtained under working conditions. It is preferably a thermal cationic initiator, particularly preferably a phosphonium salt-based thermal cationic initiator. The curing accelerator is used in an amount of usually 0.001 to 15 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the component (A) + the component (B).

In the present invention, a redox reaction in which a cleavage type photopolymerization initiator used in a radical polymerization system is used in combination is also effective. In the case of the combined system, the ease of occurrence of one electron transfer reaction determines the reactivity and the reactivity of the iodonium salt having a low level of LUMO (the lowest orbit: the basis of the ease of occurrence of electron transfer reaction) is good. Any thermosetting type photopolymerization initiator may be used, and examples thereof include 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone.

As the curing agent to be used in the present invention, it is preferable to cure at a temperature of 100 占 폚 or less in view of the reaction rate and the thermal history to the constituent member, and a thermal cationic polymerization initiator is preferably used. Further, the use of a photo cationic polymerization initiator that does not require thermal energy is also preferable.

Fine particles may be used in combination with the resin composition of the present invention, if necessary.

Examples of the fine particles include organic fine particles and inorganic fine particles. The fine particles may be used singly or in combination of plural kinds in consideration of required light transmittance, hardness, scratch resistance, curing shrinkage and refractive index.

Examples of the organic fine particles usable in the present invention include organic polymer beads such as polystyrene resin beads, acrylic resin beads, urethane resin beads and polycarbonate resin beads, porous polystyrene resin beads, porous acrylic resin beads, porous urethane resin beads, porous polycarbonate resin Porous organic polymer beads such as beads, resin powders of benzoguanamine-formalin condensates, resin powders of benzoguanamine-melamine-formalin condensates, resin powders of urea-formalin condensates, powders of aspartic acid ester derivatives, powders of zinc stearate , Powder of stearic acid amide, epoxy resin powder, polyethylene powder and the like, and crosslinked polymethyl methacrylate resin beads and crosslinked polymethyl methacrylate styrene resin beads are preferable. These organic fine particles can be easily obtained as a commercial product, or can be prepared by referring to known documents.

Examples of the inorganic fine particles usable in the present invention include conductive metal oxides, transparent metal oxides, and other inorganic fillers.

Examples of the conductive metal oxide that can be used in the present invention include zinc antimonate, tin oxide doped indium oxide (ITO), antimony doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, Tin oxide, and the like.

Examples of the transparent metal oxide that can be used in the present invention include silica, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / antimony pentoxide complex, zirconium oxide / tin oxide / Composite oxide, titanium oxide / zirconium oxide / tin oxide composite, and the like.

Examples of other inorganic fillers usable in the present invention include calcium oxide, calcium chloride, zeolite, and silica gel.

As the fine particles usable in the present invention, fine particles having excellent hardness and scratch resistance and having a high refractive index are preferable, and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / Antimony composite, zirconium oxide / tin oxide / antimony pentoxide composite, titanium oxide / zirconium oxide / tin oxide composite are preferably used. In addition, since the optical sheet used in the display is required to have a high light transmittance, the primary particle size of the fine particles is preferably 100 nm or less. The blending ratio thereof is 1 to 30 parts by mass, preferably 5 to 20 parts by mass based on 100 parts by mass of the total amount of the component (A) + the component (B).

It is also possible to use a polycarboxylic acid-based dispersant, a silane coupling agent, a titanate-based coupling agent, a silicone-based dispersant such as a modified silicone oil, a dispersant of an organic copolymerization system, or the like as a dispersant for fine particles. The blending ratio in the case of blending them is about 0.001 to 30 mass%, preferably about 0.05 to 5 mass%, based on the total mass of the resin composition of the present invention.

The primary particle diameter means the smallest particle diameter of the particles when the aggregation is collapsed. That is, in the case of the elliptical fine particles, the minor diameter is set to the primary particle diameter. The primary particle diameter can be measured by a dynamic light scattering method or an electron microscope observation. Specifically, JEOL Ltd. Product The primary particle size can be measured under the accelerating voltage of 30 kV using JSM-7700F Field Emission Scanning Electron Microscope.

These fine particles can be used dispersed in a solvent. Particularly, inorganic fine particles are easily available in the form of water or an organic solvent dispersed therein. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic alcohols such as hexane, Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl esters such as ethylene glycol monomethyl Ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol Monomethyl ether (Mono or poly) alkylene glycol monoalkyl ether monoacetates such as monoacetate, polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate and dialkyl adipate, and ether solvents such as di Examples of the solvent include alkyl ethers such as methylene chloride, ethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether Glycol ethers and cyclic ethers such as tetrahydrofuran; and ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In the resin composition of the present invention, a reactive compound other than the component (A) and the component (B) may be used in consideration of the viscosity, refractive index and adhesion of the obtained resin composition of the present invention. Specific examples of the (meth) acrylate include (meth) acrylate such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, and polyfunctional (Meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and the like.

Examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate such as cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, morpholine (Meth) acrylate, benzyl (meth) acrylate, ethoxy-modified cresol (meth) acrylate, propoxy-modified cresol (meth) acrylate, neopentyl glycol benzoate (Meth) acrylate, p-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (Meth) acrylate having an aromatic ring such as neophenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (meth) acrylate, o-phenylbenzyl acrylate, (Meth) acrylate having a heterocyclic ring such as barazol (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy (meth) acrylate, and (poly) caprolactone modified carbazole Naphthyl (meth) acrylate, naphthyl (poly) ethoxy (meth) acrylate, naphthyl (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (Meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol Acrylate, naphthol (poly) ethoxy (meth) acrylate (Meth) acrylate having a condensed ring such as naphthol (poly) propoxy (meth) acrylate and (poly) caprolactone modified naphthol (meth) acrylate, imide (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, dipropylene glycol (meth) acrylate and the like, (meth) acrylates having a hydroxyl group such as dimethylaminoethyl (meth) acrylate, butoxyethyl (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (Meth) (Meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, (Meth) acrylate such as ethoxydiethylene glycol (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol (Meth) acrylate, and the like.

Examples of the (meth) acrylate monomer having two functional groups include (meth) acrylate having a heterocycle such as hydropervalueddehyde-modified trimethylolpropane di (meth) acrylate, (poly) ethoxy-modified bisphenol A di (Poly) propoxy-modified bisphenol A di (meth) acrylate, (poly) ethoxy-modified bisphenol F di (meth) acrylate, (Meth) acrylates such as ethoxy-modified bisphenol S di (meth) acrylate, (poly) propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate and bisphenoxy (Meth) acrylate having an aromatic ring and a heterocyclic ring such as biphenyl dimethanol di (meth) acrylate, binaphthol di (meth) acrylate, binaphthol (poly) ethoxydi (Meta) acrylate having a condensed ring such as naphthol (poly) propoxydi (meth) acrylate, (poly) caprolactone modified binaphthol di (meth) acrylate, bisphenol fluorene di (Meth) acrylate such as bisphenol A (meth) acrylate, bisphenoxymethanol fluorenedi (meth) acrylate, bisphenoxyethanol fluorenedi (meth) acrylate and bisphenoxycaprolactone fluorenedio Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-hexanediol di (meth) acrylate and isocyanuric acid diacrylate, Alicyclic (meth) acrylates such as (meth) acrylate having a straight chain methylene structure such as nonanediol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate, tricyclodecane dimethanol re Di (meth) acrylates of polyhydric alcohols such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and polypropylene di .

Examples of polyfunctional (meth) acrylate monomers include multifunctional (meth) acrylate monomers having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate and (poly) caprolactone modified tris (acryloxyethyl) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy-modified pentaerythritol tetra , (Poly) caprolactone-modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy-modified dipentaerythritol penta (meth) acrylate, (poly) propoxy modified Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol (Meth) acrylate, poly (penta) ethoxylated dipentaerythritol hexa (meth) acrylate, (poly) propoxy modified dipentaerythritol hexa (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, (poly) ethoxy modified trimethylol propane tri Polyfunctional (meth) acrylates such as polyfunctional (meth) acrylates of trihydric alcohols such as tri (meth) acrylate and tri (meth) acrylate, trifunctional (meth) acrylates such as tri Acid-modified polyfunctional (meth) acrylates such as polyfunctional (meth) acrylates having an aromatic group such as 2,2,2-trisacryloyloxymethyl succinic acid, And the like silicon hexa (meth) polyfunctional (meth) acrylate having a silicone skeleton such as acrylate.

Examples of the urethane (meth) acrylate include diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxyl Diol and the like) or a polyester diol which is a reaction product of these diol compounds with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) Isocyanate (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate Chain saturated hydrocarbon isocyanates such as cyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornadiisocyanate, dicyclohexylmethane isocyanate, methylene Cyclic saturated hydrocarbon isocyanates such as bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p An aromatic polyisocyanate such as phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate or 1,5-naphthalene diisocyanate) And a reaction product obtained by adding a hydroxyl group-containing (meth) acrylate.

Examples of the polyester (meth) acrylate include a reaction product of a polyester diol and (meth) acrylic acid which are a reaction product of a diol compound and a dibasic acid or an anhydride thereof.

Among them, as the (meth) acrylate usable in the resin composition of the present invention, a material having a low hardening shrinkage ratio is preferably used. Specifically, (meth) acrylate having a cyclic structure is preferable, and isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, cyclohexyl (meth) acrylate, p-cumylphenol (poly) ethoxy (meth) acrylate, naphthol (poly) ethoxy (Meth) acrylate, benzyl (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydroxyphenyl (meth) acrylate, phenylphenol Modified trimethylol propane di (meth) acrylate, and biphenyl dimethanol di (meth) acrylate. (Meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydropaldehyde-modified trimethylolpropane di (meth) acrylate having a high Tg of the cured product and a low hardening shrinkage Biphenyl dimethanol di (meth) acrylate. In the resin composition of the present invention, the other component (meth) acrylate may be used alone or in combination of a plurality of kinds. When the (meth) acrylate is blended in the present invention, the blending amount is 10 to 200 parts by mass, preferably 50 to 150 parts by mass when 100 parts by mass of the component (A) + the component (B) is used.

When (meth) acrylate is used, it is preferable to use a photopolymerization initiator other than the photocation polymerization initiator. Specific examples include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oligo [2-hydroxy- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; Anthraquinones such as 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, and the like Pin oxide and the like. Preferably acetophenones, more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone. When the radical polymerization initiator is used, the amount is preferably from 0.1 to 10 parts by mass based on 100 parts by mass of the (meth) acrylate component. More preferably 1 to 5 parts by mass. In the resin composition of the present invention, the photopolymerization initiator may be used singly or in combination of plural kinds.

The use ratio of each component of the resin composition of the present invention can be determined in consideration of a desired refractive index, durability, viscosity, adhesion, and the like.

Usually, when the component (A) + the component (B) is 100 parts by mass, the content of the component (A) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. The content of the component (B) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. The content of the component (C) is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, in the case of a thermal cationic initiator.

The total amount of the component (A) + the component (B) is usually about 50 to 99 mass%, preferably 70 to 99 mass%, more preferably 80 to 99 mass%, based on the total amount of the resin composition of the present invention. 99% by mass, and if necessary, 90 to 99% by mass or 95 to 99% by mass. The remainder is the above-mentioned component (C) and optional addition components.

In addition to the above components, the resin composition of the present invention may further contain additives such as release agents, defoaming agents, leveling agents, light stabilizers, antioxidants, polymerization inhibitors, plasticizers, antistatic agents, etc., .

Further, in many cases, a plasticizer is used to obtain durability and flexibility. The material to be used is selected according to desired viscosity, durability, transparency, flexibility and the like. Specific examples thereof include olefin-based polymers such as polyethylene and polypropylene, aliphatic polymers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl Phthalate esters such as phthalate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate, trimellitic acid esters such as tris (2-ethylhexyl) trimellitate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (2- (2-butoxyethoxy) ethyl) adipate, bis Aliphatic dibasic acid esters such as bis (2-ethylhexyl) sebacate and diethyl succinate, trimethyl phosphate, triethyl phosphate, tributyl phosphate (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, and 2-ethylhexyldiphenyl phosphate, and methyl acetyl ricinoleate Polyesters such as ricinolic acid ester and poly (1,3-butanediol adipate), acetic acid esters such as glyceryl triacetate, sulfonamides such as N-butylbenzenesulfonamide, polyethylene glycol benzoate, polyethylene glycol dibenzoate, (Dibenzoate) such as polypropylene glycol benzoate, polypropylene glycol dibenzoate, polytetramethylene glycol benzoate and polytetramethylene glycol benzoate, polypropylene glycol, polyethylene glycol, polytetramethylene glycol and the like Of polyethers, polyethoxy-modified bisphenol A, poly Polyalkoxy-modified bisphenol F such as polyoxy-modified bisphenol F, polypropoxy-modified bisphenol F and the like, polycyclic aromatics such as naphthalene, phenanthrene and anthracene, (non-naphthol) Naphthol derivatives such as (poly) ethoxy-modified (non) naphthol, (poly) propoxy-modified (non) naphthol, (poly) tetramethylene glycol- But are not limited to, sulfide, diphenylsulfide, benzothiazolyl disulfide, diphenyl thiourea, morpholinodithiobenzothiazole, cyclohexylbenzothiazole-2-sulfenamines, tetramethylthiuram disulfide, Sulfur-containing compounds such as sulfide, sulfide, tetrabutyl thiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethylthiuram monosulfide and dipentamethylenethiuram tetrasulfide. Preferred are (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy-modified binaphthol, (poly) propoxy-modified binaphthol, diphenylsulfide.

A coupling agent may be added for the purpose of improving the adhesive strength. The coupling agent to be used is not particularly limited, but preferably contains a silane coupling agent. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxy Silane coupling agents such as silane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) Isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate Based coupling agents such as tetrabutyl titanate, tetraisopropyl di (dioctylphosphite) titanate and neoalkoxytri (pN- (p-aminoethyl) aminophenyl) titanate, Zr-acetyl acetate, Zr-methacrylate, (Neodecanoyl) zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris Zirconium or aluminum-based coupling agents such as neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate and Al-propionate are listed and used alone Or two or more of them may be used in combination. Among these coupling agents, preferred are silane coupling agents, and more preferably amino silane coupling agents or epoxy silane coupling agents. By using a coupling agent, a sealing material having excellent moisture and moisture reliability and less decrease in adhesive strength after moisture absorption can be obtained. The content of such a coupling agent is about 0.05 to 3 parts by mass based on 100 parts by mass of the reactive resin composition.

If necessary, polymers such as acrylic polymers, polyester elastomers, urethane polymers and nitrile rubbers can also be added. From the viewpoint of compatibility, it is preferable that the component having no reactive group has a weight average molecular weight of 10,000 g / mol. Further, an organic metal compound such as alkyl aluminum may be added to lower the water vapor permeability. Although a solvent may be added, it is preferable not to add a solvent.

In the resin composition of the present invention, the weight average molecular weight of each component is preferably 10,000 g / mol or less, and more preferably 5,000 g / mol or less. Since the component having a large weight average molecular weight is not dissolved, the prepared resin composition becomes a turbid liquid. This is unsuitable because the resin composition used for the display is indispensable to be uniformly transparent. In addition, excellent characteristics are required for the transmittance. Concretely, it is preferable that the light transmittance of each wavelength at a wavelength of 380 to 780 nm is 90% or more. The light transmittance can be measured by a measuring instrument such as a U-3900H spectrophotometer manufactured by Hitachi High-Technologies Corporation.

The resin composition of the present invention can be prepared by mixing and dissolving each component in accordance with a conventional method. For example, each component can be fed into a round bottom flask equipped with a stirrer and a thermometer, and stirred at 40 to 80 DEG C for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is required to be suitable for workability in the production of a display or the like, and particularly suitable for surface sealing in an organic EL device. An organic EL element is usually formed by laminating a metal electrode, an organic carrier transporting layer, an organic EL light emitting layer, an ITO electrode, and a passivation film on a substrate such as a glass substrate sequentially from the substrate side while surrounded by a dam member, A resin composition for surface encapsulation), and the surface is further sealed with a sealing substrate such as glass. The filler functions to fill a space between the substrate on the metal electrode side and the sealing substrate on the opposite side and protect the organic light emitting layer from external moisture and the like. Usually, a curable resin composition is used. After filling the resin composition , Usually a sealing substrate such as glass is loaded, the resin composition is cured, and the organic light emitting layer is sealed. The resin composition used as the filler is a resin composition for surface sealing. Therefore, it is preferable that the resin composition has a low viscosity so as to completely seal the gap between the substrates.

The viscosity is preferably measured using an E-type viscometer (TV-200, manufactured by TOKI SANGYO CO., LTD.) At 25 ° C of 1.5 Pa · s (1500 mPa · s) or less, more preferably 1300 mPa S or less, more preferably 700 mPa · s or less, and particularly preferably 400 mPa · s or less. Although there is no particular lower limit, it is usually about 50 mPa · s.

In the present invention, a resin composition containing a curing agent that causes a curing reaction with an energy ray can be easily cured by an energy ray. Specific examples of energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron rays. Among them, ultraviolet rays, laser beams, visible rays or electron beams are preferable in the present invention.

The cured product of the present invention can be obtained by irradiating the above-mentioned energy ray to the resin composition of the present invention according to the conventional method. The liquid refractive index of the resin composition of the present invention is generally from 1.45 to 1.70, preferably from 1.50 to 1.65. The refractive index can be measured by Abbe's refractometer (Model No. DR-M2, manufactured by ATAGO CO., LTD.).

The resin composition of the present invention preferably has a low shrinkage (curing shrinkage) at the time of curing, preferably 5% or less, more preferably 4% or less, and still more preferably 3.5% or less.

The cured product of the resin composition of the present invention preferably has a water vapor permeability of 50 g / m ² 24 h (measured at 60 캜 and a humidity of 90%, the same applies hereinafter) M ² · 24h or less, more preferably 30 g / m ² · 24h or less, and further preferably 30 g / m ² · 24h or less.

The glass transition temperature of the cured product is preferably higher to some extent. In the present invention, the Tg is preferably 40 ° C or higher, more preferably 45 ° C or higher, and most preferably 50 ° C or higher.

Preferred forms of the resin composition of the present invention are described below.

(i) at least one skeleton selected from the group consisting of the skeleton represented by the formula (AA), the skeleton represented by the formula (AB), the anthracene skeleton and the phenanthrene skeleton, and the oxetanyl group or the Is an aromatic compound (A) further having an epoxy group,

When the cyclic compound (B) is a group described in the following group B-2 or a group described in the following group B-3

B-2: phenyl, biphenyl, naphthalene, binaphthalene, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S,

B-3: Isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S,

And a cyclic compound or alicyclic epoxy resin further having an oxetanyl group or an epoxy group,

(A) and the cyclic compound (B) (in the case of the skeleton selected from the group described in B-2, the compound used as the aromatic compound (A) is another compound) and the curing agent (C) A resin composition for surface sealing of an organic EL device.

(ii) The resin composition according to (i), wherein any one of the aromatic compound (A) and the cyclic compound (B) contains at least an oxetanyl group or a compound having one epoxy group.

(iii) The resin composition according to (i) or (ii), wherein the aromatic compound (A) is an aromatic compound (A) having a skeleton selected from the group consisting of phenyl, biphenyl and bisphenol A as aromatic skeletons.

(iv) A resin composition according to any one of (i) to (iii), wherein the aromatic compound (A) comprises an oxetanyl group or an aromatic compound (A) having one epoxy group.

v. The resin composition according to any one of i to iv, wherein the aromatic compound (A) comprises an aromatic compound (A) having one epoxy group.

(vi) The resin composition according to any one of (i) to (v), wherein the aromatic compound (A) is o-phenylphenol glycidyl ether.

vii. The cyclic compound (B)

(a) a skeleton selected from the group consisting of phenyl, biphenyl, naphthalene, binaphthalene and bisphenol A, or

(b) a skeleton selected from the group described in (B-3) below

B-3: Isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S,

(B) having a cyclic structure represented by the following formula (I).

viii) The resin according to any one of i) to vii), wherein the cyclic compound (B) is a cyclic compound (B) having a skeleton selected from the group consisting of phenyl, biphenyl, bisphenol A, cyclopentane, cyclohexane and hydrogenated bisphenol A Composition.

ix) The resin composition according to the above viii), wherein the cyclic compound (B) is a cyclic compound (B) having a skeleton selected from the group consisting of biphenyl, bisphenol A and cyclohexane.

(x) The resin composition according to any one of (i) to (i), wherein the cyclic compound (B) is a cyclic compound (B) having at least two oxetanyl groups or epoxy groups or a limonene oxide.

xi. The resin composition according to any one of i to x above, wherein the cyclic compound (B) has a viscosity of 1,500 mPa s or less.

xii. The resin composition according to xi, wherein the cyclic compound (B) contains bisphenol A diglycidyl ether having a viscosity of not more than 1500 mPa · s.

xiii) The resin composition according to any one of i) to xii, wherein the cyclic compound (B) comprises an alicyclic epoxy resin.

xiv The resin composition according to any one of i to xiii above, wherein the resin composition has a viscosity of 1500 mPa 占 퐏 or less.

xv. The resin composition according to the above-mentioned xiv, wherein the viscosity of the resin composition is preferably 1300 mPa s or less.

(xvi) The resin composition according to any one of (i) to (xv) above, wherein the cured product having a thickness of 100 탆 and the cured product measured at 60 캜 and 90% relative humidity has a water vapor permeability of 35 g / m ² ∙ 24 hr or less.

xvii. The resin composition according to the above xvi, wherein the cured product has a vapor permeability of 30 g / m ² 24 hr or less.

xviii) The resin composition according to any one of i) to xvii, wherein the resin has a hardening shrinkage of 4% or less.

xix. The resin composition according to any one of i to xvii above, wherein the resin composition has a liquid refractive index of 1.54 to 1.7.

(xx) The resin composition according to any one of (i) to (xix), wherein the cured product of the resin composition has a glass transition point (Tg) of 45 ° C or more.

(xxi) The resin composition according to (xx) above, wherein the glass transition temperature is not lower than 50 占 폚.

xxii. The resin composition according to any one of the above i to xii wherein the ratio of the aromatic compound (A): cyclic compound (B) is 3: 7 to 7: 3.

xxiii. The resin composition according to any one of the above i to xii, wherein the ratio of the aromatic compound (A): cyclic compound (B) is 3.5: 6.5 to 6.5: 3.5.

(xxiv) The resin composition according to any one of (i) to (xii), wherein the curing agent (C) is a photo cationic polymerization initiator.

xxv Photocondensation polymerization initiator is selected from the group consisting of (tricumyl) iodonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethylphosphate and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfoniumtris [(trifluoromethyl) sulfonyl] methanide. The resin composition according to item xxiv above, wherein the compound is selected from the group consisting of

(b) a bisphenol A diglycidyl ether, a xylylene bisoxetane, a 3,3 ', 5 (b) thiophene compound having a viscosity of 1500 mPa · s or less, , 5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, biphenyl aralkyl type polyglycidyl ether, 3,4-epoxycyclohexenylmethyl- , 4'-epoxycyclohexene carboxylate, hydrogenated bisphenol A diglycidyl ether, and limonene oxide. The resin composition according to any one of the above-mentioned i to xxv.

xxvii. Bisphenol A diglycidyl ether having a viscosity of 1500 mPa 占 퐏 or less as the cyclic compound (B), 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and hydrogenated bisphenol A diglycidyl Diester and the like. The resin composition according to item xxvi above, wherein the compound is selected from the group consisting of diesters.

(xxviii) The resin composition according to any one of (i) to (xxv), wherein the aliphatic ring of the alicyclic epoxy resin in the cyclic compound (B) has 6 or 7 carbon atoms, more preferably a cyclohexane ring.

A solid sealing method of an organic EL device according to the present invention includes a step of forming a passivation film on an organic EL element formed on a substrate, a step of applying a resin composition for surface sealing on the passivation film, And a step of curing the resin composition for surface encapsulation, wherein the curable resin composition according to the present invention is used as the resin composition for encapsulation.

The organic EL element to be sealed comprises a substrate, a lower electrode, an organic EL layer including at least a light emitting layer, and an element body including an upper electrode. The substrate is provided with a transparent substrate made of a glass substrate, a cycloolefin or polycarbonate, polymethyl methacrylate, or the like, or a flat substrate made of an electrically insulating material such as an organic / inorganic hybrid transparent substrate in which the transparent organic material is made high- Lt; / RTI > The following are typical examples of the constitution of the element unit main body.

(1) Lower electrode / light emitting layer / upper electrode

(2) lower electrode / electron transporting layer / light emitting layer / upper electrode

(3) Lower electrode / light emitting layer / hole transporting layer / upper electrode

(4) lower electrode / electron transporting layer / light emitting layer / hole transporting layer / upper electrode

For example, in the organic EL device having the layer structure of (4), a lower electrode (cathode) made of an Al-Li alloy or the like is formed on one surface of a substrate by a resistance heating deposition method or a sputtering method, An electron transport layer composed of an oxadiazole derivative or a triazole derivative or the like, a light-emitting layer, Nd-diphenyl-N, N'-bis (3-methylphenyl) -1,1- -diamine or the like and a top electrode (anode) sequentially by a thin film forming method such as a resistance heating deposition method or an ion beam sputtering method. The layer structure or material of the organic EL element is not particularly limited as long as it functions as a display element. Further, the solid sealing method according to the present invention can be applied to any organic EL element having any structure.

The passivation film is formed so as to cover the organic EL element. The passivation film can be formed by an inorganic material such as silicon nitride or silicon oxide by vapor deposition or sputtering. The passivation film is provided to prevent moisture, ionic impurities, and the like from entering the organic EL device. The thickness of the passivation film is preferably in the range of 10 nm to 100 탆, and more preferably in the range of 100 nm to 10 탆. The passivation film may be laminated for the purpose of enhancing reliability.

The passivation film may be an incomplete film having pinholes in general, or a film having weak mechanical strength in many cases, depending on the film forming method. Therefore, in the solid sealing method, an adhesive is further applied on the passivation film, the adhesive is compressed by using a sealing transparent substrate, and the reliability of the sealing is enhanced by curing the adhesive.

Example

EXAMPLES The present invention will be described in further detail with reference to the following examples. The present invention is not limited at all by the following examples. The numerical unit "part" represents the mass part.

The ultraviolet-curing resin compositions and the respective cured products of the examples and comparative examples were obtained in the compositions shown in the following examples and comparative examples. The evaluation method and evaluation criteria for the resin composition and the cured film were as follows.

(1) Viscosity: Measured at 25 캜 using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(2) Liquid refractive index: The refractive index (25 DEG C) of the resin composition to which the resin composition was added was measured by Abbe's refractive index meter (DR-M2: manufactured by ATAGO CO., LTD.).

(3) Water vapor transmission rate: into the energy radiation or a thermosetting resin, a glass substrate, to adjust the film thickness by using the 100㎛ of the spacer, a high pressure mercury lamp (80W / cm, an ozone-less) to 3000mJ / cm ² or 100 ℃ 1hr To prepare a test piece. The obtained test pieces were measured for moisture permeability at 60 占 폚 占 90% RH by Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois).

(4) Tg (glass transition point): The Tg point of the cured energy ray or thermosetting resin layer was measured with a viscoelasticity measuring system EXSTAR DMS-6000 (manufactured by SII NANOTECHNOLOGY CO., LTD.), A tensile mode and a frequency of 1 Hz.

(5) Curing shrinkage: An energy ray or thermosetting resin layer was applied on a substrate, and irradiated with 3000 mJ / cm ² by a high-pressure mercury lamp (80 W / cm, ozone resistance) To prepare a cured product for measuring the specific gravity of the film.

The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B method. The specific gravity (DL) of the resin composition was measured at 23 占 占 폚, and the curing shrinkage ratio was calculated by the following formula. The measurement result is expressed by an average value of four measurement results.

Cure shrinkage (%) = (DS-DL) / DS x 100

(6) Processability:

KAYATORON Z-5536 (thickness: 5 mu m) was coated on a clean glass substrate using a dispenser (SHOTMASTER: manufactured by Musashi Engineering, Inc.).

Subsequently, the resin compositions of Examples and Comparative Examples were dropped into a seal pattern range using a dispenser in the same manner as the seal pattern.

Another piece of clean glass substrate was adhered and adhered to the resin composition dropping completed substrate in a vacuum using an apparatus. Thereafter, a gap was formed in the atmosphere to form a gap, and the mixture was cured by UV irradiation (cumulative light amount: 3000 mJ / cm ² ), placed in an oven at 120 ° C and heated and cured for 1 hour to prepare an evaluation sample.

Evaluation standard

○ ... The dropping liquid quickly spreads within the cell, and the resin composition is uniformly filled in the cell without gaps.

△ ... The spread of the dropping liquid into the cell is slightly slower, but the resin composition is uniformly filled in the cell without the liver.

× ... The dropping liquid does not sufficiently spread in the cell, a gap is formed in the cell, and the resin composition is not uniformly filled.

OPP-G: SANKO CO., LTD. Products o-Phenyl phenol glycidyl ether

OXT-121: Toagosei Company, Limited Products Xylenylene Bisoxetane

jER-828: product of Mitsubishi Chemical Corporation bisphenol A diglycidyl ether

EP-4088S: product of ADEKA CORPORATION dicyclopentadiene dimethanol diglycidyl ether

YX-4000H: product of Mitsubishi Chemical Corporation 3,3 ', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl

KAYARAD NC-3000H manufactured by Nippon Kayaku Co., Ltd. Biphenyl aralkyl type polyglycidyl ether

SEJ-01R manufactured by Nippon Kayaku Co., Ltd. 3,4-Epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate

GSID 26-1: manufactured by BASF Japan Co., Ltd. (tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl]

Epolite 4000: KYOEISHA CHEMICAL CO., LTD. The product hydrogenated bisphenol A diglycidyl ether

Limonene oxide: Lemon oxide from RENESSENZ

Epolite 80MF: KYOEISHA CHEMICAL CO., LTD. Products Glycerine diglycidyl ether

Epolite 100MF: KYOEISHA CHEMICAL CO., LTD. Product trimethylol propane triglycidyl ether:

As clearly shown from the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 3, the resin composition of the present invention having a specific composition has a high Tg, a low curing shrinkage ratio, and a low water vapor permeability. Therefore, it is suitable, for example, for a coating agent for a barrier film and various sealing materials, particularly a surface sealing material of an organic EL element.

(Industrial applicability)

INDUSTRIAL APPLICABILITY The resin composition and the cured product of the present invention are suitable for various sealing materials, particularly, surface sealing materials for organic EL devices, because they have excellent visible light transmittance and light fastness, high Tg, and low curing shrinkage and steam permeability.

Claims (25)

At least one skeleton selected from the group consisting of a skeleton represented by formula (AA) of the following (i), a skeleton represented by formula (AB) below, an anthracene skeleton and a phenanthrene skeleton, (A) having an epoxy group, and a cyclic compound (B) having an oxetanyl group or an epoxy group and satisfying the following condition (iii) and having a viscosity of not more than 1300 mPa.s Wherein the resin composition for surface sealing of the organic EL device is a resin composition for surface sealing of an organic EL device.
(i) a skeleton represented by formula (AA)

[Wherein X represents a direct bond, a sulfur atom or a dimethylmethylene group, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 4]
(ii) a skeleton represented by formula (AB)

[Wherein R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4]
(iii) Conditions of cyclic compound (B):
When the ring in the cyclic compound (B) is an aromatic ring, an aliphatic ring or a hetero ring, and among them, when the ring is an aromatic ring, the cyclic compound has a structure different from that of the compound used as the aromatic compound (A) (B) an alicyclic compound, the cyclic compound is an alicyclic hydrocarbon skeleton having a crosslinked structure or a cyclic compound having a cycloalkylene skeleton and an oxetanyl group or an epoxy group or an alicyclic epoxy resin. The method according to claim 1,
The aromatic resin (A) has a skeleton selected from the group described in the following (A-1).
A-1: phenyl, biphenyl, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S 3. The method according to claim 1 or 2,
The aromatic compound (A) is an aromatic skeleton, and is a compound having a skeleton selected from the group consisting of phenyl, biphenyl and bisphenol A. 4. The method according to any one of claims 1 to 3,
Wherein the cyclic compound (B) has a ring selected from the group described in the following (B-1).
B-1: an aromatic ring, the aliphatic ring and the heterocycle The method according to claim 1,
Wherein the cycloalkylene skeleton forms a skeleton represented by the following formula (BA).

[Wherein Y represents a direct bond, a sulfur atom or a methylene group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and t represents an integer of 1 to 4] The method according to claim 1,
Wherein the cyclic compound (B) is an alicyclic epoxy resin. 5. The method according to any one of claims 1 to 4,
Wherein the ring of the cyclic compound (B) is an aromatic ring. 8. The method of claim 7,
The cyclic compound (B) has a skeleton selected from the group described in the following (B-2).
B-2: phenyl, biphenyl, naphthalene, binaphthalene, anthracene, phenanthrene, bisphenol A, bisphenol F and bisphenol S 9. The method of claim 8,
Wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of phenyl, biphenyl, naphthalene, binaphthalene and bisphenol A, or an epoxy compound. 5. The method according to any one of claims 1 to 4,
The cyclic compound (B) has a skeleton selected from the group described in the following (B-3).
B-3: Isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S 11. The method according to claim 4 or 10,
The cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of adamantane, cyclohexane, and hydrogenated bisphenol A. 5. The method according to any one of claims 1 to 4,
The cyclic compound (B) has a skeleton selected from the group described in the following (B-4).
B-4: morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine 13. The method according to claim 4 or 12,
The cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of oxane, dioxane and triazine. 14. The method according to any one of claims 1 to 13,
A resin composition for surface sealing of an organic EL device, which further comprises a curing agent (C). 15. The method of claim 14,
A resin composition for surface sealing of an organic EL device, wherein the curing agent (C) is a photo cationic polymerization initiator. 16. The method of claim 15,
Wherein the photo cationic polymerization initiator is at least one selected from the group described in the following (C-1).
C-1: sulfonium salts, iodonium salts, phosphonium salts, ammonium salts and antimonates 15. The method of claim 14,
A resin composition for surface sealing of an organic EL device, wherein the curing agent (C) is a heat curing agent. 18. The method of claim 17,
The resin composition for surface sealing of an organic EL device according to (C-2), wherein the thermosetting agent is selected from the group of (C-2) below.
C-2: amine compound, acid anhydride compound, amide compound, phenol compound, carboxylic acid compound, imidazole compound, isocyanuric acid adduct, metal compound, sulfonium salt, ammonium salt, antimonate, Phonium salt, microcapsule type hardener 19. The method according to any one of claims 1 to 18,
Wherein the aromatic compound (A) is contained in an amount of 20 to 80 parts by mass based on 100 parts by mass of the total amount of the aromatic compound (A) and the cyclic compound (B). 20. The method according to any one of claims 1 to 19,
Wherein the cyclic compound (B) is contained in an amount of 20 to 80 parts by mass based on 100 parts by mass of the total amount of the aromatic compound (A) and the cyclic compound (B). 21. The method according to any one of claims 1 to 20,
Wherein the curing agent (C) is contained in an amount of 0.1 to 5 parts by mass when the total amount of the aromatic compound (A) and the cyclic compound (B) is 100 parts by mass. 22. The method according to any one of claims 1 to 21,
Wherein the cured product has a water vapor permeability of 35 g / m ² .24 hr or less as measured at 60 캜 and a relative humidity of 90% as a cured product having a thickness of 100 탆. An organic EL display characterized by being sealed with a cured product obtained by curing a resin composition for surface sealing of the organic EL device according to any one of claims 1 to 22. A film for surface sealing of an organic EL display, characterized by having a barrier property obtained by applying and curing a resin composition for surface sealing of the organic EL device according to any one of claims 1 to 22 on a substrate. Use of the resin composition for surface sealing of an organic EL device according to any one of claims 1 to 22 for surface sealing of an organic EL device.