CN105073799A - Energy ray-curable resin composition and cured product of same - Google Patents

Abstract

A resin composition comprising a (meth)acrylate compound (A) having an alicyclic hydrocarbon backbone, a cyclic (meth)acrylate compound (B), and a polymerization initiator (C), wherein the cyclic (meth)acrylate compound (B) is a (meth)acrylate compound different from said compound (A), and is at least one (meth)acrylate compound selected from the group consisting of (meth)acrylate compounds having an alicyclic hydrocarbon backbone and (meth)acrylate compounds having a heterocyclic backbone.

Description

Energy ray curable resin composition and cured product thereof

Background technique

Energy ray-curable resins can generally be processed without solvents, so they are excellent in workability. In addition, energy ray curing technology is an important technology in various industries including display peripheral materials because of its fast curing speed and low energy requirements. In recent years, among displays, a thin display called a flat panel display (FPD), especially a plasma display (PDP) and a liquid crystal display (LCD) have been put into the market and widely used. In addition, organic electroluminescent (EL) displays (OLEDs) are expected as next-generation self-luminous thin-film displays, and some products have already been put into practical use. An organic EL element of an organic EL display has a structure in which an element part main body including a thin film laminate 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. Layers such as the light-emitting layer and electrodes of the element part are easily degraded by moisture or oxygen, and the deterioration causes a reduction in luminance, lifespan, and discoloration. Therefore, the organic EL element is sealed to block intrusion of moisture or impurities from the outside. In order to realize a high-quality and highly reliable organic EL element, a higher-performance sealing material has been desired, and various sealing technologies have been studied.

As a typical sealing method of organic EL elements, a method of fixing a metal or glass sealing cap inserted with a desiccant in advance to a substrate of an organic EL element with a sealing adhesive has been studied (Patent Document 1). In this method, an adhesive is applied to the outer periphery of a substrate of an organic EL element, a sealing cap is placed thereon, and the adhesive is cured to fix the substrate and the sealing cap to seal the organic EL element. Among such methods, sealing with a glass sealing cap is the mainstream. However, the glass sealing cover tends to be expensive because it is manufactured by performing a drilling process for inserting a desiccant into a flat glass substrate. In addition, in sealing with the sealing cap, since a desiccant is inserted inside the sealing cap, light cannot be extracted from the sealing cap side. That is, the extraction of light emitted from the light source from the substrate side of the device is limited to bottom emission type devices. In the case of a bottom emission type element, there are problems of a decrease in aperture ratio due to a driver circuit portion formed on a substrate, and a decrease in extraction efficiency due to a part of light being blocked by the driver circuit portion. Therefore, it is desired to develop a sealing method applicable to a top emission type element that extracts light from the opposite side of the substrate of the organic EL element.

As representative sealing methods applicable to top emission type elements, there are film sealing method and solid sealing method. The thin-film sealing method is a method of forming a passivation film by laminating a plurality of thin films made of inorganic or organic materials on an organic EL element (Patent Document 2). In order to impart sufficient moisture resistance to the device by this method, it is necessary to sequentially laminate several layers of thin films on the device. Therefore, in the thin film sealing method, the film forming process is long and the cost is high, and the initial investment tends to be high due to the introduction of large-scale vacuum system equipment required for film forming.

On the other hand, in the solid sealing method, a passivation film is provided so as to cover the entire element portion of the organic EL element, and a transparent substrate for sealing is provided thereon via a sealing material (see Patent Document 3). Usually, a passivation film is formed by vapor deposition or sputtering of an inorganic material, but it is often a defective film having pinholes or a film having weak mechanical strength. Therefore, in the solid sealing method, after providing a passivation film on an element, a transparent substrate for sealing such as a glass substrate is provided through an adhesive for sealing, thereby improving the reliability of sealing. Such a solid sealing method has attracted attention as a method capable of sealing a top-emission type element simply and at low cost.

In the sealing of organic EL elements by the solid sealing method, heat or photocurable resins can be used as sealing adhesives, but their characteristics are very important because they may have a significant impact on the performance of the element and the productivity of the sealing work. . For example, if the water vapor transmission rate of the adhesive for sealing is insufficient, it may intrude into the element part from the pinholes of the passivation film, resulting in deterioration of the element. In addition, if the curing reaction of the sealing material is slow, the curing process will take time, and the productivity of the sealing work may decrease.

For sealing adhesives used in these, in addition to high transmittance in the visible light region, light resistance to withstand light emission, stable formability, low cure shrinkage for suppressing residual stress, and Low water vapor transmission rate to protect light-emitting elements from moisture, etc. It is possible to use a known adhesive as an adhesive for sealing organic EL elements and perform sealing by a solid sealing method, but it is currently difficult to obtain a result that satisfies reliability, productivity, and water vapor transmission rate, and it is desired to develop a product suitable for the solid sealing method adhesive for sealing.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3876630

Patent Document 2: Japanese Patent No. 2679586

Patent Document 3: Japanese Patent No. 4421938

Patent Document 4: Japanese Patent No. 4655172

Patent Document 5: Japanese Patent Laid-Open No. 2001-81182

Patent Document 6: Japanese Patent Laid-Open No. 2000-169552

Contents of the invention

The problem to be solved by the invention

An object of the present invention is to provide a resin composition suitable for use as a sealing material for an organic EL element, and a cured product of the resin composition having excellent visible light transmittance, curing shrinkage, moisture permeability, and low brittleness.

means of solving problems

The inventors of the present invention conducted extensive and intensive studies to solve the above-mentioned problems, and as a result, found that an energy ray-curable resin composition having a specific composition and a cured product thereof can solve the above-mentioned problems, and completed the present invention.

That is, the present invention relates to the following (1) to (9).

(1) A resin composition comprising a (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton, a cyclic (meth)acrylate compound (B) and a polymerization initiator (C), wherein,

The cyclic (meth)acrylate compound (B) is a (meth)acrylate compound different from the compound (A), and is selected from (meth)acrylate compounds having an alicyclic hydrocarbon skeleton and hetero At least one (meth)acrylate compound in the group consisting of ring skeleton (meth)acrylate compounds.

(2) The resin composition according to (1), wherein the (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton is (meth)acrylic acid having two or more alicyclic hydrocarbon skeletons in one molecule ester compounds.

(3) The resin composition as described in (1) or (2), wherein the alicyclic hydrocarbon skeletons in the (meth)acrylate compounds each having an alicyclic hydrocarbon skeleton are bicyclodecane skeletons, tricyclodecane skeletons, and tricyclodecane skeletons respectively. alkane skeleton or adamantane skeleton.

(4) The resin composition according to (1) or (2), wherein the (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton is (meth)acrylic acid represented by the following formula (1) ester compound,

In the formula, R ₁ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a halogen atom or the following formula (2), and at least one R ₁ is the following formula (2),

In the formula, R ₂ represents a direct bond or a (poly)alkyleneoxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a ring skeleton.

(5) The resin composition according to (1) or (2), wherein the (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton is (meth)acrylic acid represented by the following formula (3) ester compound,

In the formula, R ₃ and R ₄ represent a direct bond, or an alkylene or alkyleneoxy group having 1 to 6 carbon atoms.

(6) The resin composition according to any one of (1) to (5), wherein the cyclic (meth)acrylate compound (B) is a (meth)acrylate compound having a heterocyclic skeleton, The (meth)acrylate compound having a heterocyclic skeleton is a (meth)acrylate compound represented by the following formula (4),

In the formula, R ₅ each independently represent a direct bond, or an alkylene or alkyleneoxy group with 1 to 6 carbon atoms, R ₆ each independently represent hydrogen or an alkyl group with 1 to 4 carbon atoms, and Z each independently independently represent a methylene group, an oxygen atom or a nitrogen atom, but not all of Z are methylene groups.

(7) The resin composition as described in (6), wherein the (meth)acrylate compound (A) represented by the above formula (1): a cyclic (meth)acrylic acid represented by the above formula (4) The weight ratio of ester (B) is 9:1-1:9.

(8) A low moisture permeability barrier film obtained by curing the resin composition described in any one of (1) to (7).

(9) The resin composition as described in any one of (1)-(7), which is used for OLED use.

Invention effect

The resin composition of the present invention and its cured product have excellent visible light transmittance, low cure shrinkage, moisture permeability and brittleness, and are therefore particularly suitable for use as a sealing material for organic EL elements.

Detailed ways

The resin composition of this invention contains the (meth)acrylate compound (A) which has an alicyclic hydrocarbon skeleton, a cyclic (meth)acrylate compound (B), and a polymerization initiator (C).

With the above constitution, two kinds of (meth)acrylate compounds with different skeletons are mutually introduced into the curing system during curing, and while achieving low shrinkage, it is possible to achieve extremely Excellent low water vapor transmission rate effect.

In addition, the skeleton described in the present invention may or may not have a substituent, and when it has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. or an alkenyl group having 1 to 6 carbon atoms.

As the (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton that can be used in the present invention, known (meth)acrylate compounds having an alicyclic hydrocarbon skeleton, alicyclic hydrocarbon The skeleton is preferably a saturated hydrocarbon skeleton. Compared with other skeletons such as chain-like skeletons, such a cyclic skeleton has the effect of preventing water vapor from permeating. Prevent the penetration of water vapor.

As the alicyclic hydrocarbon skeleton, specifically usable skeletons include a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a bicyclodecane skeleton, a tricyclodecane skeleton, an adamantane skeleton, and an isobornyl skeleton. wait.

Among these, (meth)acrylate compounds having bridged ring hydrocarbon skeletons such as tricyclodecane skeleton and adamantane skeleton are preferable. In such a compound, since bridges are formed on the alicyclic hydrocarbon skeleton, a three-dimensional structure is formed and carbon atoms are arranged in the space of the ring structure, so that the permeation of water vapor can be more effectively prevented. And the said synergistic effect becomes higher by mixing with the (meth)acrylate compound which has such a bridged ring type hydrocarbon frame|skeleton.

In addition, it is preferable that the (meth)acryloyl group is bonded to the cyclic hydrocarbon skeleton. Specifically, it is preferable that the (meth)acryloyl group is directly or via a hydrocarbon group connected to the above-mentioned cyclic hydrocarbon skeleton. As the hydrocarbon group when connected via a hydrocarbon group, an alkylene group having 1 to 10 carbon atoms or a carbon atom having an ether bond can be mentioned. An alkylene group with a number of 1 to 10.

Specific examples of the (meth)acrylate compound having such an alicyclic hydrocarbon skeleton include the following monofunctional (meth)acrylate compounds and bifunctional or higher (meth)acrylate compounds.

Examples of monofunctional (meth)acrylate compounds include isobornyl (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, dihydrodicyclopentadiene (meth)acrylate, Alkenyl esters, dihydrodicyclopentadienyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1, 3-Adamantane dimethanol di(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylate base) alicyclic (meth)acrylates such as 3-hydroxy-1-adamantyl acrylate and 1-adamantyl (meth)acrylate. Alicyclic (meth)acrylates, such as tricyclodecane dimethanol (meth)acrylate, etc. are mentioned as a bifunctional or more polyfunctional (meth)acrylate compound.

As the (meth)acrylate compound having such a cyclic hydrocarbon skeleton, a (meth)acrylate compound having a structure represented by the following formula (1) can preferably be used.

In the formula, R ₁ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a halogen atom or the following formula (2), and at least one R ₁ is the following formula (2),

In the formula, R ₂ represents a direct bond or a (poly)alkyleneoxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a ring skeleton.

In addition, a (meth)acrylate compound represented by the following formula (3) may preferably be used.

In the formula, R ₃ and R ₄ represent a direct bond, or an alkylene or alkyleneoxy group having 1 to 6 carbon atoms. Here, as a specific example of such a (meth)acrylate compound, alicyclic (meth)acrylates, such as tricyclodecane dimethanol (meth)acrylate, etc. are mentioned.

The content of the (meth)acrylate compound having an alicyclic hydrocarbon skeleton in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 parts by weight relative to 100 parts by weight of the resin composition. ~70 parts by weight.

As a cyclic (meth)acrylate (B) used for this invention, the (meth)acrylate which has an alicyclic hydrocarbon skeleton, and the (meth)acrylate which has a heterocyclic skeleton can be used.

Here, when a (meth)acrylate compound having an alicyclic hydrocarbon skeleton is used as a cyclic (meth)acrylate compound, the resin composition will contain (meth)acrylate compounds having two different structures. ) a resin composition of an acrylate compound. Moreover, the (meth)acrylate compound similar to the above can be used as (meth)acrylate which has an alicyclic hydrocarbon skeleton which can be used as a cyclic (meth)acrylate.

When two kinds of (meth)acrylate compounds having an alicyclic hydrocarbon skeleton are used in this way, compared with other skeletons such as chain structure skeletons, it has the effect of preventing water vapor from permeating, and by combining with (meth)acrylate compounds having an alicyclic hydrocarbon skeleton ( The meth)acrylate compounds are configured together in the curing system, and the synergistic effect can significantly prevent the penetration of water vapor.

The (meth)acrylate compound which has a heterocyclic frame|skeleton which can be used as a cyclic (meth)acrylate compound in this invention is demonstrated below.

Compared with other skeletons such as chain structure skeletons, such a heterocyclic skeleton has the effect of preventing water vapor from permeating. The effect can significantly prevent the penetration of water vapor.

As a heterocyclic skeleton, a dioxane skeleton, a trioxane skeleton, an isocyanurate skeleton, etc. are mentioned as a concrete usable skeleton.

In addition, it is preferable that the (meth)acryloyl group is bonded to the heterocyclic skeleton. Specifically, it is preferable that a (meth)acryloyl group is directly or via a hydrocarbon group bonded to the above-mentioned heterocyclic skeleton. Examples of the hydrocarbon group when bonding via a hydrocarbon group include an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms having an ether bond. ~10 alkyl groups.

As a specific example of the (meth)acrylate compound which has such a heterocyclic skeleton, the following (meth)acrylate compound is mentioned.

That is, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, iso Cyanuric acid EO modified diacrylate (M-215), ε-caprolactone modified tris(acryloyloxyethyl) isocyanurate (M-327), isocyanuric acid EO modified diacrylate Acrylates and triacrylates (M-313 or M-315), hydroxypivalaldehyde-modified trimethylolpropane diacrylate (R-604), pentamethylpiperidinyl methacrylate (FA-711) , Tetramethylpiperidinyl methacrylate (FA-712HM), Cyclic trimethylolpropane formal acrylate (SR531).

As such a (meth)acrylate compound having a heterocyclic skeleton, examples of a heterocyclic ring include: a morpholine skeleton, a tetrahydrofuran skeleton, an oxane skeleton, a dioxane skeleton, and a triazine skeleton. Skeleton, carbazole skeleton, pyrrolidine skeleton, piperidine skeleton, preferably, a (meth)acrylate compound having a structure represented by the following formula (5) can be used.

In the formula, R ₅ each independently represent a direct bond, or an alkylene or alkyleneoxy group with 1 to 6 carbon atoms, R ₆ represents a hydrogen atom, or an alkyl or alkenyl group with 1 to 4 carbon atoms, X each independently represents a nitrogen atom, an oxygen atom or a methylene group, Y each independently represents a methylene group or a carbonyl group, and m represents an integer of 1 to 4, but not all of X are methylene groups.

Here, preferably, a compound represented by the following formula (4) can be used.

In the formula, R ₅ each independently represent a direct bond, or an alkylene or alkyleneoxy group with 1 to 6 carbon atoms, R ₆ each independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, Z Each independently represents a methylene group, an oxygen atom or a nitrogen atom. However, not all of Z are methylene groups.

The content of the (meth)acrylate compound having a heterocyclic skeleton in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 100 parts by weight relative to 100 parts by weight of the resin composition. 70 parts by weight.

Regarding the resin composition of the present invention, among the (meth)acrylate compound components in the resin composition, a (meth)acrylate compound (hereinafter referred to as polyEO) having a structure represented by the following partial structural formula (A) is preferable. The total weight of the modified (meth)acrylate compound) is less than the total weight of the (meth)acrylate compounds other than the polyEO-modified (meth)acrylate compound, more preferably 1/2 or less. This is because the water vapor transmission rate of the above-mentioned polyEO-modified (meth)acrylate compound is poor, and when the content of the polyEO-modified (meth)acrylate compound is large and predominates in the resin composition, Possibly poor water vapor transmission rate.

In the formula, t represents an integer of 2 or more.

Furthermore, the total weight of the polyEO-modified (meth)acrylate compound in the resin composition is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, particularly preferably 2 parts by weight or less, based on 100 parts by weight of the resin composition. .

In the present invention, as a cyclic (meth)acrylate compound and as a polyEO-modified (meth)acrylate compound, a cyclic polyEO-modified (meth)acrylate compound is preferably not used as the present invention. A (meth)acrylate compound or a cyclic (meth)acrylate compound of an aromatic hydrocarbon skeleton is used, so even if it is used, it is preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, based on 100 parts by weight of the resin composition. .

In the present invention, the ratio of the alicyclic hydrocarbon skeleton-containing (meth)acrylate (A) to the cyclic (meth)acrylate compound (B) contained in the resin composition is preferably 1:9 to 1:9 by weight. 9:1, more preferably 7:3 to 9:1, particularly preferably 5:5 to 9:1.

By setting it as the said preferable range, the resin composition excellent in water vapor transmission rate can be obtained.

Various polymerization initiators, such as a photoinitiator and a thermal radical polymerization initiator, can be used as a polymerization initiator (C) used by this invention.

In addition, examples of photopolymerization initiators specifically include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; , 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2 -Methylphenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinylpropan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] and other acetophenones; 2-ethylanthracene Anthraquinones such as quinone, 2-tert-butyl anthraquinone, 2-chloroanthraquinone, 2-pentyl anthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Thioxanthone and other thioxanthones; ketals such as acetophenone dimethyl ketal and bibenzoyl dimethyl ketal; benzophenone, 4-benzoyl-4'-methyldiphenylsulfide Ether, 4,4'-dimethylaminobenzophenone and other benzophenones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethyl Phosphine oxides such as benzoyl)-phenylphosphine oxide and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide; etc. Preferred are acetophenones, and more preferred examples include 2-hydroxy-2-methylphenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone. In addition, in the resin composition of this invention, a photoinitiator can be used individually or in mixture of multiple types.

In addition, the thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, and examples thereof include organic peroxides, azo compounds, benzoin compounds, and benzoin ether compounds. , acetophenone compound, benzopinacol, etc., preferably use benzopinacol. For example, Kayamek (trademark) A, M, R, L, LH, SP-30C, Perkadox (trademark) CH-50L, BC-FF, Cadox (trademark) B-40ES, Perkadox (trademark) as organic peroxides 14. Trigonox (trademark) 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester (trademark) P-70, TMPO-70, CND-C70, OO- 50E, AN, Kayabutyl (trademark) B, Perkadox16, Kayacarbon (trademark) BIC-75, AIC-75 (manufactured by Kayaku Akuzo Co., Ltd.), Permek (trademark) N, H, S, F, D, G, Perhexa ( Trademark) H, HC, TMH, C, V, 22, MC, Percure (trademark) AH, AL, HB, Perbutyl (trademark) H, C, ND, L, Percumyl (trademark) H, D, Peroyl (trademark) IB, IPP, Perocta (trademark) ND (manufactured by NOF Corporation), etc. are commercially available. Moreover, VA-044, V-070, VPE-0201, VSP-1001 etc. (made by Wako Pure Chemical Industries, Ltd.) which are azo compounds are commercially available.

As the thermal radical polymerization initiator, a benzopinacol-based thermal radical polymerization initiator (including chemically modified benzopinacol) is preferable. Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2- Tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4- Methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethylsilyloxy base)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsilyloxy)-1,1,2,2-tetraphenylethane, 1,2- Bis(tert-butyldimethylsilyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1,1,2,2- Tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy -1,1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2 -Triethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1,1,2,2-tetraphenyl 1,2-bis(trimethylsilyloxy)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsilyloxy-1 , 1,2,2-tetraphenylethane, 1,2-bis(trimethylsilyloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis( Trimethylsilyloxy)-1,1,2,2-tetraphenylethane.

The aforementioned benzopinacol is sold by Tokyo Kasei Kogyo Co., Ltd., Wako Pure Chemical Industry Co., Ltd., and the like. In addition, the etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. In addition, the hydroxysilyl etherification of benzopinacol can be synthesized by heating the corresponding benzopinacol and various silylating agents under a basic catalyst such as pyridine. As the silylating agent, trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N,O-bis(tri Methylsilyl)trifluoroacetamide (BSTFA), triethylchlorosilane (TECS) as triethylsilylating agent, tert-butylmethylsilane as tert-butyldimethylsilylating agent (TBMS) etc. These reagents are readily commercially available from silicon derivative manufacturers and the like. The reaction amount of the silylation agent is preferably 1.0 to 5.0 times mole with respect to 1 mole of the hydroxyl group of the target compound. More preferably, it is 1.5-3.0 times mole. When the amount is less than 1.0 times mole, the reaction efficiency is poor and the reaction time is long, so thermal decomposition may be promoted. When the amount is more than 5.0 times mole, the separation may be poor during recovery or purification may be difficult.

The content of the component (C) of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. In addition, in the resin composition of this invention, a polymerization initiator (C) can be used individually or in mixture of multiple types.

As the (meth)acrylate compound (D) optionally contained in the resin composition of the present invention, as long as it is a (meth)acrylate compound having at least one aromatic ring in the molecule, it can be Any known compound can be used arbitrarily. In such a compound having an aromatic ring, since it has an aromatic ring, water repellency can be imparted to the resin composition, and the water vapor transmission rate can be reduced. And this effect can be fully realized if it is a (meth)acrylate compound which has one or more aromatic rings in a molecule|numerator. Moreover, since this effect is more excellent by having two or more aromatic rings in a molecule|numerator, it is preferable. Examples of the skeleton having two or more aromatic rings in such a molecule include a biphenyl skeleton and a bisphenol skeleton, and these skeletons can be realized to exhibit an excellent water vapor transmission rate.

Specific examples of the (meth)acrylate compound having such an aromatic hydrocarbon skeleton include the following monofunctional (meth)acrylate compounds and bifunctional or higher (meth)acrylate compounds.

Examples of monofunctional (meth)acrylate compounds include: benzyl (meth)acrylate, ethoxy-modified cresol (meth)acrylate, propoxy-modified cresol (meth)acrylate ester, neopentyl glycol benzoate (meth)acrylate, o-phenylphenol (meth)acrylate, o-phenylphenol monoethoxy (meth)acrylate, o-phenylphenol polyethoxylate p-phenylphenol (meth)acrylate, p-phenylphenol monoethoxy (meth)acrylate, p-phenylphenol polyethoxy (meth)acrylate, acrylic acid Monocyclic (meth)acrylate compounds such as o-phenylbenzyl ester and p-phenylbenzyl acrylate; carbazole (poly)ethoxy (meth)acrylate, carbazole (poly)propoxy (Meth)acrylate, (poly)caprolactone-modified carbazole (meth)acrylate and other heterocyclic (meth)acrylate compounds; (meth)naphthyl acrylate, (poly)ethoxy Naphthyl (meth)acrylate, (poly)propoxynaphthyl (meth)acrylate, (poly)caprolactone modified naphthyl (meth)acrylate, binaphthol (meth)acrylate, binaphthyl Phenol (poly)ethoxy (meth)acrylate, binaphthol (poly)propoxy (meth)acrylate, (poly)caprolactone modified binaphthol (meth)acrylate, naphthol (Meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthol (methyl) (meth)acrylate compounds having condensed rings, such as ) acrylates.

Examples of (meth)acrylate compounds with more than bifunctionality include: (poly)ethoxy-modified bisphenol A di(meth)acrylate, (poly)propoxy-modified bisphenol A di(meth)acrylate ) acrylate, (poly)ethoxy modified bisphenol F di(meth)acrylate, (poly)propoxy modified bisphenol F di(meth)acrylate, (poly)ethoxy modified Bisphenol S di(meth)acrylate, (poly)propoxy modified bisphenol S di(meth)acrylate, hexahydrophthalic acid di(meth)acrylate, bisphenoxy (poly ) ethoxyfluorene and other monocyclic (meth)acrylate compounds; biphenyl dimethanol di(meth)acrylate and other heterocyclic (meth)acrylate compounds; binaphthol di(methyl) Acrylate, binaphthol (poly) ethoxy di (meth) acrylate, binaphthol (poly) propoxy di (meth) acrylate, (poly) caprolactone modified binaphthol di ( (meth)acrylate compounds with condensed rings such as methacrylates; bisphenol fluorene di(meth)acrylate, bisphenoxymethanol fluorene di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate Polycyclic aromatic (meth)acrylate compounds such as (meth)acrylate, bisphenoxycaprolactone fluorene di(meth)acrylate, and the like.

Examples of the (meth)acrylate compound having an aromatic hydrocarbon skeleton include epoxy (meth)acrylate compounds other than the above-mentioned (meth)acrylate monomers.

Examples of epoxy (meth)acrylate include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl type phenol aralkyl resin, bisphenol A Reaction products of epoxy resins such as terminal glycidyl ethers of propylene oxide adducts, fluorene epoxy resins, and bisphenol S-type epoxy resins with (meth)acrylic acid, etc.

Among them, as the (meth)acrylate compound having an aromatic hydrocarbon skeleton, specifically, for example, a (meth)acrylate compound having a partial skeleton described below can be preferably used.

In the formula, X represents a direct bond or an alkylene group having 1 to 3 carbon atoms.

It is considered that the water repellency imparted by the aromatic ring can be more effectively expressed by having the above partial skeleton.

Specifically, among the above-mentioned (meth)acrylate compounds, a (meth)acrylate compound having a bisphenol skeleton or a biphenyl skeleton corresponds to the above-mentioned formula (B), and can be preferably used.

In addition, it is preferable that the (meth)acryloyl group is bonded to the aromatic hydrocarbon skeleton. Specifically, it is preferable that the (meth)acryloyl group is directly or via a hydrocarbon group connected to the above-mentioned aromatic hydrocarbon skeleton. As the hydrocarbon group when connected via a hydrocarbon group, an alkylene group having 1 to 10 carbon atoms or a carbon number having an ether bond can be mentioned. 1 to 10 alkylene groups.

Moreover, as a (meth)acrylate compound which has an aromatic hydrocarbon skeleton used by this invention, the (meth)acrylate compound represented by following formula (7) is preferable.

In the formula, X represents a direct bond or an alkylene group with 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R represents a hydrogen atom, an alkyl group with ₁ to 3 carbon atoms, a halogen atom or the following formula ( ₂ ), R2 represents a direct bond or a (poly)alkyleneoxy group with 1 to 10 carbon atoms;

In the formula, R ₂ represents a direct bond or a (poly)alkyleneoxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a benzene skeleton.

Specific examples of such (meth)acrylate compounds include o-phenylphenol (meth)acrylate, o-phenylphenol monoethoxy (meth)acrylate, o-phenylphenol polyethoxy ( Meth)acrylate, p-phenylphenol (meth)acrylate, p-phenylphenol monoethoxy (meth)acrylate, p-phenylphenol polyethoxy (meth)acrylate, acrylic ortho-phenyl phenylbenzyl ester, p-phenylbenzyl acrylate, (poly)propoxy modified bisphenol A di(meth)acrylate, (poly)ethoxy modified bisphenol F di(meth)acrylate , (poly)propoxy modified bisphenol F di(meth)acrylate, etc.

The content of the (meth)acrylate compound having an aromatic hydrocarbon skeleton in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 100 parts by weight relative to 100 parts by weight of the resin composition. 70 parts by weight.

In addition, in the resin composition of the present invention, considering the viscosity, refractive index, adhesiveness, etc. of the obtained resin composition of the present invention, other than (meth)acrylate compounds (A) having an alicyclic hydrocarbon skeleton can be used. (meth)acrylate compounds other than the cyclic (meth)acrylate compound (B) and the (meth)acrylate compound (D) which has an aromatic hydrocarbon frame|skeleton. Specifically, (meth)acrylate monomers can be cited. As the (meth)acrylate monomers, monofunctional (meth)acrylates, difunctional (meth)acrylates, and three Polyfunctional (meth)acrylates of the above (meth)acryloyl groups, polyester (meth)acrylates, epoxy (meth)acrylates, and the like.

Examples of monofunctional (meth)acrylates include: imide (meth)acrylate having an imide ring structure; butanediol mono(meth)acrylate, (meth)acrylate 2-hydroxyl Ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dipropylene glycol (meth)acrylate, etc. Base) acrylates; dimethylaminoethyl (meth)acrylate, butoxyethyl (meth)acrylate, caprolactone (meth)acrylate, isobutyl (meth)acrylate, (meth) ) tert-butyl acrylate, octafluoropentyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, etc. Alkyl (meth)acrylate; Ethoxydiethylene glycol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, polyethylene glycol (meth)acrylate, Polyol (meth)acrylates such as polypropylene glycol (meth)acrylate, etc.

Examples of (meth)acrylate monomers having two functional groups include: acrylated products of isocyanates such as diacrylated isocyanurate; 1,4-butanediol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. have a linear methylene structure (Meth)acrylate; ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Alcohol di(meth)acrylate, etc.

Examples of polyfunctional (meth)acrylate monomers include tris(acryloyloxyethyl)isocyanurate, (poly)caprolactone-modified tris(acryloyloxyethyl)isocyanurate, ) esters and other polyfunctional (meth)acrylates with isocyanurate rings; pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, (poly)ethoxy modified pentaerythritol tetra(meth)acrylate base) acrylate, (poly)propoxy modified pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, (poly)caprolactone modified dipentaerythritol penta(meth)acrylate, (Poly)ethoxy-modified dipentaerythritol penta(meth)acrylate, (poly)propoxy-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (poly)hexyl Lactone modified dipentaerythritol hexa(meth)acrylate, (poly)ethoxy modified dipentaerythritol hexa(meth)acrylate, (poly)propoxy modified dipentaerythritol hexa(meth)acrylate, Polypentaerythritol multi(meth)acrylate, Trimethylolpropane tri(meth)acrylate, (poly)ethoxylated trimethylolpropane tri(meth)acrylate, (poly)propoxy Polyfunctional (meth)acrylic acid modified polyols such as trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, glycerin tri(meth)acrylate, etc. Phosphorus-containing polyfunctional (meth)acrylates such as tri(meth)acrylate phosphate; polyfunctional (meth)acrylates with aromatic groups such as trimethylolpropane benzoate (meth)acrylate Acrylates; acid-modified polyfunctional (meth)acrylates such as 2,2,2-triacryloyloxymethylsuccinic acid; polysiloxane hexa(meth)acrylates with polysiloxane Skeleton polyfunctional (meth)acrylate, etc.

Such (meth)acrylate monomers other than (meth)acrylate compound (A), (meth)acrylate compound (B), (meth)acrylate compound (D) are contained in the resin composition The content of the compound is preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight relative to 100 parts by weight of the resin composition.

In the present invention, urethane (meth)acrylate can be used to the extent that the properties are not impaired.

Examples of urethane (meth)acrylates include glycol compounds (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butane Diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol , polyethylene glycol, polypropylene glycol, bisphenol A polyethoxy glycol, bisphenol A polypropoxy glycol, etc.) or as these diol compounds with dibasic acids or their anhydrides (for example, succinic acid, hexanoic acid Polyester diols of reaction products of diacid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or their anhydrides), and organic polyisocyanates (for example, tetramethylene chain saturated hydrocarbon isocyanate such as diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; Phorne diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc. Cyclic saturated hydrocarbon isocyanate; 2,4-toluene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, Aromatic polyisocyanates such as 6-isopropyl-1,3-phenyl diisocyanate and 1,5-naphthalene diisocyanate), reaction products obtained by adding hydroxyl-containing (meth)acrylate, etc.

The content of the urethane (meth)acrylate compound in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, particularly preferably 20 to 70 parts by weight, based on 100 parts by weight of the resin composition. parts by weight.

In the present invention, fine particles may be appropriately contained in the resin composition. Examples of fine particles include organic fine particles and inorganic fine particles. In addition, fine particles (E) may be used alone or in combination of multiple types in consideration of desired light transmittance, hardness, scratch resistance, cure shrinkage, and refractive index.

In addition, from the viewpoint of improving transmittance (in particular, transmittance at 380 nm to 780 nm), it is preferable not to contain fine particles.

In addition, the glass transition temperature of the resin composition of the present invention is preferably 70°C or higher, particularly preferably 100°C or higher.

As organic microparticles that can be used in the present invention, organic polymer pellets such as polystyrene resin pellets, acrylic resin pellets, polyurethane resin pellets, and polycarbonate resin pellets; porous polystyrene resin pellets; Porous organic polymer pellets such as balls, porous acrylic resin pellets, porous polyurethane resin pellets, porous polycarbonate resin pellets; resin powder of benzoguanamine-formaldehyde condensate, benzoguanamine-melamine- Formaldehyde condensate resin powder, urea-formaldehyde condensate resin powder, aspartic acid ester derivative powder, zinc stearate powder, stearamide powder, epoxy resin powder, polyethylene powder, etc., preferably cross-linked Polymethyl methacrylate resin pellets, cross-linked polymethyl methacrylate-styrene resin pellets, etc. These organic fine particles can be easily obtained as commercial items, and can also be prepared by referring to known documents.

Examples of inorganic fine particles that can be used in the present invention include conductive metal oxides, transparent metal oxides, and other inorganic fillers.

Examples of conductive metal oxides 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, fluorine-doped tin oxide, etc.

Examples of transparent metal oxides that can be used in the present invention include silica, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/antimony pentoxide composite, Zirconia/tin oxide/antimony pentoxide composite, titanium oxide/zirconia/tin oxide composite, etc.

Calcium oxide, calcium chloride, zeolite, silica gel, etc. are mentioned as another inorganic filler which can be used in this invention.

Fine particles that can be used in the present invention are preferably fine particles that are excellent in hardness and scratch resistance and have a high refractive index, and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide can be preferably used /antimony pentoxide composite, zirconia/tin oxide/antimony pentoxide composite, titanium oxide/zirconia/tin oxide composite. In addition, since high light transmittance is required for an optical sheet used in a display, the primary particle diameter of the fine particles is preferably 100 nm or less. The compounding ratio of these is preferably 1-30 mass parts with respect to 100 mass parts of total amounts of component (A)+component (B), More preferably, it is 5-20 mass parts.

In addition, polysiloxane-based dispersants such as polyvalent carboxylic acid-based dispersants, silane coupling agents, titanate-based coupling agents, modified silicone oils, organic copolymer-based dispersants, and the like may be used in combination as a dispersant for fine particles. The compounding ratio of these is about 0-30 mass % with respect to the gross mass of the resin composition of this invention, Preferably it is about 0.05-5 mass %.

It should be noted that the primary particle size refers to the smallest particle size that the particles have when they are dispersed and aggregated. That is, in the case of elliptical particles, the minor axis is defined as the primary particle diameter. The primary particle size can be measured by a dynamic light scattering method, electron microscope observation, or the like. Specifically, the primary particle diameter can be measured using a JSM-7700F field emission scanning electron microscope manufactured by JEOL Ltd. under the condition of an accelerating voltage of 30 kV.

In the present invention, the primary particle diameter is preferably 100 nm or less. Further, fine particles having a primary particle diameter of 5 nm to 100 nm can be preferably used. When the primary particle diameter is 100 nm or less, scratch resistance can be imparted and a cured product with high transmittance can be provided.

These fine particles can be used dispersed in a solvent. In particular, inorganic fine particles are readily available as commercial products in the form of being dispersed in water or an organic solvent, and examples of the organic solvent used include hydrocarbon solvents, ester solvents, ether solvents, and ketone solvents. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and petroleum ether, unleaded gasoline, and solvents that are mixtures thereof. Naphtha, etc. Examples of ester solvents include: alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate (mono or poly)alkylene glycol monoalkyl ether monoacetates such as esters, butanediol monomethyl ether monoacetate; dialkyl glutarate, dialkyl succinate, adipic acid Polycarboxylic acid alkyl esters such as dialkyl esters, etc. Examples of ether solvents include: diethyl ether, ethyl butyl ether and other alkyl ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, Glycol ethers such as methyl ether and triethylene glycol diethyl ether; cyclic ethers such as tetrahydrofuran, etc. As a ketone solvent, acetone, methyl ethyl ketone, cyclohexanone, isophorone, etc. are mentioned.

When fine particles are used in the present invention, the content of the fine particles is usually preferably 0.001 to 20 parts by weight, more preferably 0.001 to 10 parts by weight, particularly preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the resin composition.

In the resin composition of the present invention, in addition to the above-mentioned components, in order to improve the convenience of handling, etc., a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, Plasticizers, antistatic agents, etc.

In addition, there are many cases where plasticizers are used to obtain durability and flexibility. The material used is selected according to desired viscosity, durability, transparency, flexibility, and the like. Specifically, for example: olefin polymers such as polyethylene and polypropylene; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethyl phthalate) Hexyl) ester, diisodecyl phthalate, benzyl butyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalate glycolate Phthalate esters such as acyl ethyl ester and butyl glycolate phthaloyl butyl ester; trimellitate esters such as tris(2-ethylhexyl) trimellitate; dibutyl adipate, Diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis(2-(2-butoxy) adipate Ethoxy)ethyl) ester, di(2-ethylhexyl) azelate, dibutyl sebacate, di(2-ethylhexyl) sebacate, diethyl succinate and other aliphatic Dibasic esters; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, Orthophosphates such as cresyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; ricinoleic acid esters such as acetyl ricinoleic acid methyl ester; poly(1,3-butylene adipate), etc. Polyesters; Acetates such as glycerol triacetate; Sulfonamides such as N-butylbenzenesulfonamide; Polyethylene glycol benzoate, polyethylene glycol dibenzoate, polypropylene glycol benzoate, poly Propylene glycol dibenzoate, polytetramethylene glycol benzoate, polytetramethylene glycol dibenzoate and other polyalkylene oxide (di) benzoate; polypropylene glycol, polyethylene glycol Alcohol, polytetramethylene glycol and other polyethers; polyethoxy-modified bisphenol A, polypropoxy-modified bisphenol A and other polyalkoxy-modified bisphenol A; polyethoxy-modified bisphenol F, polyalkoxy modified bisphenol F such as polypropoxy modified bisphenol F; polycyclic aromatic compounds such as naphthalene, phenanthrene, anthracene; (bi) naphthol, (poly) ethoxy modified (co) Naphthol, (poly) propoxy modified (bin) naphthol, (poly) tetramethylene glycol modified (bin) naphthol, (poly) caprolactone modified (bin) naphthol and other naphthols Derivatives; diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, diphenylthiourea, morpholinodithiobenzothiazole, cyclohexylbenzothiazole-2-sulfenamide , Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetra(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide , Sulfur-containing compounds such as bispentamethylene thiuram tetrasulfide. Preferable examples include (poly)ethylene glycol dibenzoate, (poly)propylene glycol dibenzoate, binaphthol, (poly)ethoxy-modified binaphthol, (poly)propoxy-modified bis-naphthol, Naphthol, diphenyl sulfide.

In addition, polymers such as acrylic polymers, polyester elastomers, urethane polymers, and nitrile rubbers may be added as needed.

The organic compound component having no reactive group preferably has a weight average molecular weight of 10000 g/mol or less, particularly preferably 5000 g/mol or less, from the viewpoint of compatibility. In the present invention, the content of the organic compound without a reactive group in the resin composition is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, particularly preferably 0.5% by weight or less, based on the resin composition. By setting it to 1.5% by weight or less, it is possible to prevent components without reactive groups from being incompatible and remaining in the form of insoluble components such as solids or gels, so that the transparency and durability of cured products can be prevented. Since heat property deteriorates, it is preferable. In addition, in order to reduce the water vapor transmission rate, an organometallic compound such as an aluminum alkyl may be added. It is also possible to add a solvent, but preferably no solvent is added.

The resin composition of the present invention preferably has excellent properties in terms of transmittance, and specifically, the transmittance at each wavelength in the wavelength range of 380 nm to 780 nm is preferably 90% or more. The light transmittance can be measured with a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Tech Co., Ltd.

The resin composition of the present invention can be prepared by mixing and dissolving components according to a conventional method. For example, it can be obtained by putting each component into a round-bottomed flask equipped with a stirring device and a thermometer, and stirring at 20 to 80°C, preferably 40 to 80°C, for 0.5 to 6 hours.

Regarding the viscosity of the resin composition of the present invention, as a viscosity suitable for workability, a composition having a viscosity of 1000 mPa·s or less at 25° C. measured using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.) is preferable. , particularly preferably 500 mPa·s or less.

The resin composition of the present invention can be easily cured by energy rays. Here, specific examples of energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, and laser rays; particle rays such as α-rays, β-rays, and electron beams; and the like. In the present invention, among these energy rays, ultraviolet rays, laser rays, visible light, or electron rays are preferable.

The cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the above-mentioned energy rays according to a conventional method. The liquid refractive index of the resin composition of this invention is 1.45-1.55 normally, Preferably it is 1.48-1.52. The refractive index can be measured with an Abbe refractometer (model: DR-M2, manufactured by Atago Co., Ltd.) or the like.

The resin composition of the present invention has a water vapor transmission rate at 60°C with a thickness of 100 μm of preferably 200 g/m ² ·day or less, more preferably 100 g/m ² ·day or less, particularly preferably 60 g/m ² ·day or less . By adjusting to this range, it is possible to effectively prevent damage to the element due to the penetration of moisture.

The solid sealing method of the organic EL element using the resin composition of the present invention preferably includes the steps of: forming a passivation film on the organic EL element formed on the substrate; coating an adhesive for sealing on the passivation film, and a step of providing a transparent substrate for sealing; and a step of curing the adhesive for sealing. The above curable resin composition of the present invention can be used as an adhesive for sealing.

The organic EL element to be sealed is composed of, for example, a substrate, and an element portion main body including a lower electrode, an organic EL layer including at least a light-emitting layer, and an upper electrode. Use glass substrates, transparent organic materials including cycloolefin, polycarbonate, polymethyl methacrylate, etc., organic/inorganic hybrid transparent substrates obtained by making the transparent organic materials highly rigid with glass fibers, etc., including electrical insulation The flat substrate of the active substance is used as the substrate. In addition, the following structures are mentioned as a typical structure of an element part main body.

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

(2) Lower electrode/Electron transport layer/Emitting layer/Upper electrode

(3) Lower electrode/luminescent layer/hole transport layer/upper electrode

(4) Lower electrode/electron transport layer/light emitting layer/hole transport layer/upper electrode

For example, an organic EL element having the layer structure of the above (4) can be formed by forming a lower electrode (cathode) containing an Al-Li alloy or the like on one side of a substrate by resistance heating evaporation or sputtering, and then vaporizing it by resistance heating. Thin film formation methods such as plating or ion beam sputtering are sequentially stacked including Electron transport layers such as oxadiazole derivatives and triazole derivatives, light-emitting layers, hole transport layers made of TPD or the like, and upper electrodes (anodes) are produced as organic EL layers. In addition, the layer structure and material of an organic EL element will not be specifically limited as long as it functions as a display element. In addition, the resin composition of the present invention can be applied to organic EL elements of any structure.

The passivation film is formed to cover the organic EL element. The passivation film can be formed by evaporation or sputtering using inorganic materials such as silicon nitride and silicon oxide. The passivation film is provided to prevent moisture, ionic impurities, etc. from intruding into the organic EL element. The thickness of the passivation film is preferably in the range of 10 nm to 100 μm, more preferably in the range of 100 nm to 10 μm.

Although it depends on the film-forming method, a passivation film is generally a defective film with pinholes, and it is a film with weak mechanical strength in many cases. Therefore, in the solid sealing method using the resin composition of this invention, the adhesive agent is further apply|coated on a passivation film, it press-bonds using the transparent board|substrate for sealing, and hardens the adhesive agent, thereby improving the reliability of sealing.

Example

Next, the present invention will be described in more detail by way of examples. The present invention is not limited in any way by the following examples. In addition, the unit "part" of a numerical value represents a mass part.

According to the compositions shown in Examples 1 to 5 and Comparative Examples 1 to 2 in Table 1 (the values are "parts"), the ultraviolet curable resin composition of the present invention and the comparative ultraviolet curable resin composition and their compositions were obtained. Cured. In addition, the evaluation method and evaluation standard about the resin composition and hardened|cured material were performed as follows. In addition, the evaluation was performed after fully volatilizing the organic solvent with the evaporator about the Example containing an organic solvent.

(1) Moisture permeability: The ultraviolet curable resin is sandwiched between glass substrates with a thickness of 5 mm, the film thickness is adjusted with a spacer of 100 μm, and cured with a high-pressure mercury lamp (120 W/cm, ozone-free) at 3000 mJ/cm ² to produce test piece. About the obtained test piece, the water vapor transmission rate under 60 degreeC*90%RH conditions was measured using Lyssy water vapor permeability meter L80-5000 (made by Systech Illinois company). The results are shown in Table 1.

(2) Tg (glass transition temperature): The Tg point of the cured ultraviolet curable resin layer was measured with a viscoelasticity measurement system EXSTARDMS-6000 (manufactured by SI INano Technology Co., Ltd.) in tension mode at a frequency of 1 Hz. The results are shown in Table 1.

(3) Brittleness: On easy-adhesive PET (A4300 100 μm thick: manufactured by Toyobo Co., Ltd.), use a Meyer bar coater (メイヤーバークーター) to coat with a thickness of 20 μm, and use a high-pressure mercury lamp (80W /cm, no ozone) was irradiated at 3000mJ/cm ² to cure and obtain a test piece. Then, evaluation was performed by bending the test piece by 180°.

(4) Transmittance: The ultraviolet curable resin was sandwiched between glass substrates, the film thickness was adjusted using a 60 μm spacer, and it was cured at 3000 mJ/cm ² with a high-pressure mercury lamp (120 W/cm, ozone-free) to prepare a test piece. The obtained test piece was measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Co., Ltd.) with a measurement range of 780 to 380 nm, a light source C, and a viewing angle of 2°, and the transmittance at 400 nm was recorded.

(5) Curing shrinkage rate: From the liquid specific gravity before curing at 25° C. and the film specific gravity at 25° C. obtained by curing, the curing shrinkage rate was calculated using the following mathematical formula (1). In addition, as the test piece of cure shrinkage rate, the test piece cured by the same method as the test piece of moisture permeability was used.

Curing shrinkage rate = (film specific gravity - liquid specific gravity) / film specific gravity × 100 (1)

Table 1

Adamantatem-104: Adamantyl methacrylate, manufactured by Idemitsu Kosan Co., Ltd.

R-684: Tricyclodecane dimethanol acrylate, manufactured by Nippon Kayaku Co., Ltd.

R-604: Hydroxypivalaldehyde-modified trimethylolpropane diacrylate, manufactured by Nippon Kayaku Co., Ltd.

UR203: Liquid polyisoprene, manufactured by Kuraray Corporation

NIKANOLY-50: Reaction product of m-xylene and formaldehyde (number average molecular weight 250), manufactured by Fudow Co., Ltd.

Irgacure184D: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation

As a result of the measurement, it was confirmed that in all of Examples 1 to 5, no cracks occurred in the brittleness test, all the transmittances were 90% or more, and the curing shrinkage rate was as low as 3 to 4%.

From the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 2, it can be seen that the resin composition of the present invention having a specific composition has a high Tg, and low moisture permeability and cure shrinkage. Therefore, it is suitably used for various sealing materials, especially the sealing material of an organic EL element, for example.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

In addition, this application is based on the JP Patent application (2013-072059) of an application on March 29, 2013, The whole is used by reference. In addition, all the references cited here are incorporated in this specification as a whole.

Industrial applicability

The resin composition of the present invention and its cured product have excellent visible light transmittance, high Tg, low moisture permeability, brittleness and curing shrinkage, so they are suitable for various sealing materials, especially organic EL element sealing materials.

Claims (9)

1. a resin combination, it contains (methyl) acrylic compound (A), ring-type (methyl) acrylic compound (B) and the polymerization starter (C) with alicyclic hydrocarbon skeleton, wherein,

Ring-type (methyl) acrylic compound (B) is (methyl) acrylic compound different from described compound (A), and for being selected from least one (methyl) acrylic compound in the group that is made up of (methyl) acrylic compound with alicyclic hydrocarbon skeleton and (methyl) acrylic compound with heterocyclic skeleton.

2. resin combination as claimed in claim 1, wherein, has (methyl) acrylic compound (A) of alicyclic hydrocarbon skeleton for having (methyl) acrylic compound of two or more alicyclic hydrocarbon skeleton in a part.

3. resin combination as claimed in claim 1 or 2, wherein, the alicyclic hydrocarbon skeleton respectively had in (methyl) acrylic compound of alicyclic hydrocarbon skeleton is dicyclo decane skeleton, tricyclodecane skeleton or adamantane framework separately.

4. resin combination as claimed in claim 1 or 2, wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (1),

In formula, R ₁represent the alkyl of hydrogen atom, carbonatoms 1 ~ 3, halogen atom or following formula (2) independently of one another, and at least one R ₁for following formula (2),

In formula, R ₂represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10, Y represents hydrogen atom or methyl, * and cyclic skeleton bonding.

5. resin combination as claimed in claim 1 or 2, wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (3),

In formula, R ₃and R ₄represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6.

6. the resin combination according to any one of Claims 1 to 5, wherein, ring-type (methyl) acrylic compound (B) is for having (methyl) acrylic compound of heterocyclic skeleton, (methyl) acrylic compound with heterocyclic skeleton is (methyl) acrylic compound represented by following formula (4)

In formula, R ₅represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6 independently of one another, R ₆represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another, Z represents methylene radical, Sauerstoffatom or nitrogen-atoms independently of one another, but Z is not all methylene radical.

7. resin combination as claimed in claim 6, wherein, (methyl) acrylic compound (A) represented by above formula (1): the weight ratio of ring-type (methyl) acrylate (B) represented by above formula (4) is 9:1 ~ 1:9.

8. a low moisture-inhibiting barrier film, it obtains by making the resin composition according to any one of claim 1 ~ 7.

9. the resin combination according to any one of claim 1 ~ 7, it is for OLED purposes.