阅读说明：本技术 硬化性组合物及化合物 (Curable composition and compound ) 是由 秋池利之 鬼丸奈美 于 2019-08-08 设计创作，主要内容包括：本发明涉及一种作为可应用于显示装置、照明装置等途的有机电致发光元件的密封材料而有用的硬化性组合物及化合物,目的在于提供一种在维持作为密封材的硬化性能的同时,折射率高,且涂布性、透明性优异的硬化性组合物。进而,目的在于提供一种如下的硬化性组合物,其为低粘度,且所得到的硬化膜也适合作为耐蚀刻性优异的压印材料。为了解决所述课题而完成的发明是包含(A)下述式(1)所表示的化合物、(B)聚合引发剂的硬化性组合物,所述硬化性组合物中,相对于硬化性组合物的100质量份,在20质量份至99质量份的范围内包含(A)成分。(The present invention relates to a curable composition and a compound useful as a sealing material for an organic electroluminescent element applicable to a display device, an illumination device, and the like, and aims to provide a curable composition having a high refractive index and excellent coatability and transparency while maintaining the curing performance as a sealing material. Further, it is an object to provide a curable composition which has a low viscosity and gives a cured film suitable as a stamping material having excellent etching resistance. The invention made to solve the above problems is a curable composition containing (a) a compound represented by the following formula (1) and (B) a polymerization initiator, wherein the curable composition contains the component (a) in a range of 20 to 99 parts by mass per 100 parts by mass of the curable composition.)

1. A curable composition comprising:

(A) a compound represented by the following formula (1);

(B) a polymerization initiator, and

the curable composition is characterized in that it is,

the curable composition contains the component (A) in the range of 20 to 99 parts by mass relative to 100 parts by mass of the curable composition;

in the formula (1), X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group; n is an integer of 2 or 3, m is an integer representing the relationship 0. ltoreq. m.ltoreq.8-n; y is a single bond or a sulfur atom.

2. The curable composition according to claim 1, wherein the viscosity of the curable composition is in the range of 3 to 30 mPas at 25 ℃.

3. The curable composition according to claim 1 or 2, further comprising a polymerizable compound other than the component (A) as the component (C).

4. The curable composition according to claim 3, wherein said component (C) is a vinyl sulfide derivative, a (meth) acrylate derivative, a vinyl sulfoxide derivative or a vinyl sulfone derivative.

5. The curable composition according to claim 1 or 2, further comprising particles having a particle diameter of 10nm or more and 100nm or less as the component (D).

6. The hardening composition according to claim 5, wherein the particles are at least one selected from metal oxide particles and hollow particles.

7. The curable composition according to claim 1 or 2, wherein a sealing film for an organic electroluminescent element is formed.

8. The curable composition according to claim 1 or 2, which is used for a composition for imprints.

9. A compound represented by the following formula (2);

Technical Field

The present invention relates to a curable composition and a compound useful as a sealing material and a stamping (imprint) material for an organic electroluminescent element applicable to applications such as a display device and an illumination device.

Background

In order to protect an object or the like with a cured product, various curable materials have been proposed as curable compositions for forming a cured product. For example, as one of elements for electronic devices which have been developed in recent years, an organic Electroluminescence (EL) element having a laminated structure including an anode, an organic light emitting layer, and a cathode is known.

However, since the light-emitting material contained in the organic light-emitting layer is easily deteriorated by moisture and oxygen, it is necessary to seal the organic EL element. Therefore, element sealing using a curable composition is known for protecting the organic light-emitting layer (patent document 1). In addition, since light emission of the organic EL element occurs in the element, various methods are used to extract the light, and generally, the light extraction efficiency is improved by adjusting the refractive index of each layer from the light emitting layer to the outermost layer (patent document 2).

In order to reduce damage to an organic EL element in sealing the element, a curing composition free of firing and solvent is desired, and photo-curing is desirable (patent document 3). In addition, from the viewpoint of saving the liquid, the inkjet coating method is becoming widespread, and a low-viscosity hardening composition is desired as inkjet coating suitability.

However, the cured product described in patent document 3 is not suitable for inkjet coating because of its high viscosity, although it can be cured by light.

As described above, a curable composition having photo-curing properties, no solvent, low viscosity, and a high refractive index is required as a sealing material for an organic EL device.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2014-225380

[ patent document 2] Japanese patent No. 5395677 publication

[ patent document 3] Japanese patent No. 5479248 publication

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention aims to provide a curable composition which improves the reliability of the organic EL element, reduces the ink-jet coatability and the occurrence of cracks in inorganic films such as transparent electrodes, has no solvent and low viscosity, and gives a cured film having a high refractive index. Further, it is an object of the present invention to provide a curable composition which has a low viscosity and gives a cured film having excellent etching resistance.

[ means for solving problems ]

The present inventors have made diligent studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a curable composition having the following structure, and have completed the present invention.

The invention

(1) The curable composition is obtained by including (A) a compound represented by the following formula (1) and (B) a polymerization initiator, wherein the curable composition contains the component (A) in a range of 20 to 99 parts by mass relative to 100 parts by mass of the curable composition.

[ solution 1]

In the formula (1), X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group. n is an integer of 2 or 3, and m is an integer representing the relationship 0. ltoreq. m.ltoreq.8-n. Y is a single bond or a sulfur atom.

(2) Further, the curable composition according to (1) has a viscosity in the range of 3 to 30 mPas at 25 ℃.

(3) The curable composition of (1) or (2), further comprising a polymerizable compound other than the component (A) as the component (C).

(4) The curable composition according to any one of (1) to (3), wherein the component (C) is a vinyl sulfide derivative, a (meth) acrylate derivative, a vinyl sulfoxide derivative or a vinyl sulfone derivative.

(5) The curable composition according to any one of (1) to (4), which further comprises particles having a particle diameter of 10nm or more and 100nm or less as the component (D).

(6) The curable composition according to any one of (1) to (5), wherein the particles are at least one selected from metal oxide particles and hollow particles.

(7) The curable composition according to any one of (1) to (6), which is used for forming a sealing film of an organic EL element.

(8) The curable composition according to any one of (1) to (6), which is used for a composition for imprinting.

(9) The compound is represented by the following formula (2).

[ solution 2]

[ Effect of the invention ]

Further, according to the present invention, there can be provided a curable composition which is excellent in wet spreadability on a substrate in ink-jet coating, is less in coating unevenness, is less in cracking (cracking) of an inorganic film such as a transparent electrode, and is less in outgas (outgas) after curing. Further, since the cured film has a high refractive index while maintaining the sealing performance, the light extraction efficiency can be improved. Further, by utilizing such characteristics, the resin composition is excellent in curability, refractive index and etching resistance, and can be suitably used as a material for imprinting used for manufacturing optical parts.

Detailed Description

The curable composition of the present invention is a curable composition comprising (a) a compound represented by formula (1) and (B) a polymerization initiator, wherein the curable composition contains the component (a) in a range of 20 to 99 parts by mass per 100 parts by mass of the curable composition. The details thereof will be described below.

Compound (A)

The compound (A) of the present invention is a naphthalene compound having 2 or more vinyl groups in 1 molecule represented by the following formula (1). Is a compound having a structure in which a vinyl group is directly bonded to a benzene ring of naphthalene.

[ solution 3]

In the formula (1), X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group. n is an integer of 2 or 3, and m is an integer representing the relationship 0. ltoreq. m.ltoreq.8-n.

The vinyl group of the present invention is directly bonded to the benzene ring. At least one aromatic hydrocarbon group having a vinyl group is present in one molecule, and preferably two or more aromatic hydrocarbon groups are present.

The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, or the like. The alkoxy group having 1 to 6 carbon atoms is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, or the like.

Specific examples of the compound (a) include: 1, 3-divinylnaphthalene, 1, 4-divinylnaphthalene, 1, 5-divinylnaphthalene, 1, 6-divinylnaphthalene, 1, 7-divinylnaphthalene, 2, 3-divinylnaphthalene, 2, 6-divinylnaphthalene, 2, 7-divinylnaphthalene, 1,2, 4-trivinylnaphthalene, 1,2, 6-trivinylnaphthalene, 1, 3-divinyl-6-methoxy-naphthalene, 1, 3-divinyl-6-methyl-naphthalene, 1, 3-divinyl-6-chloro-naphthalene, 1, 2-divinyl-6-ethoxy-naphthalene, 1-vinyl-5-methoxy-naphthalene, 1, 5-divinyl-naphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like.

When Y in formula (1) is a sulfur atom, examples thereof include (VS-1) and (VS-2) shown in the following formulae.

[ solution 4]

Of these, preferred are 1, 3-divinylnaphthalene, 1, 4-divinylnaphthalene, 1, 6-divinylnaphthalene, 1, 7-divinylnaphthalene, 2, 3-divinylnaphthalene, 1,2, 4-trivinylnaphthalene, 1,2, 6-trivinylnaphthalene, 1-vinyl-5-methoxy-naphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene.

These vinylnaphthalenes are prepared by reacting

The first stage is as follows: a step of converting the compound into a halogen such as trifluoromethanesulfonate (triflate) or bromine,

and a second stage: divinyl naphthalene can be synthesized by a step of coupling a triflate or a halogen with a vinyl compound.

Triflation of the phenol group of naphthalene enables the synthesis of triflic anhydride by action. Further, the bromination can be synthesized by allowing phosphorus tribromide to act on a hydroxyl group, or can be performed by brominating phosphorus with bromine using an amine compound as a starting compound.

Examples of the coupling in the second stage are: a method of Coupling vinyltributyltin using a palladium catalyst (refer to journal of organic chemistry (j. org. chem.), 1993, volume 58, pages 7388 to 7892 (bamboos et al)), a method of Coupling vinylborate using a palladium catalyst, a method of Coupling vinylmagnesium chloride using a palladium catalyst, a method of Coupling vinyltrialkoxysilane to Hiyama Coupling, and the like. Among these methods, a method of coupling vinyltributyltin or a vinylborate is particularly preferable.

[ solution 5]

The vinyl sulfides represented by the formulae (VS-1) and (VS-2) can be obtained by, for example, reacting a thiol with 1, 2-dibromoethane to synthesize a sulfide, and then removing hydrogen bromide with potassium hydroxide.

[ solution 6]

The amount of the compound (a) to be used is preferably in the range of 20 to 99 parts by mass, particularly preferably in the range of 50 to 90 parts by mass, with respect to 100 parts by mass of the curable composition, and is preferably in view of viscosity and volatility of the curable composition.

< (B) polymerization initiator

The polymerization initiator preferably used in the present invention is preferably a photoinitiator, and examples thereof include a photoradical initiator and an acid generator. The polymerization initiator (B) of the present invention contains 1 to 10% by mass of the curable composition.

Examples of the photo radical initiator include: o-acyloxime compounds, acetophenone compounds, bisimidazole compounds, and the like.

Specific examples of the O-acyloxime compounds include preferred O-acyloxime compounds: 1- [ 9-ethyl-6- (2-methylbenzoyl) -9.H ] -carbazol-3-yl ] -ethane-1-ketoxime-O-acetate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzoyl) -9.h. -carbazol-3-yl ] -1- (O-acetyloxime) or ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9.h. -carbazol-3-yl ] -1- (O-acetyloxime).

These O-acyloxime compounds may be used alone or in combination of 2 or more.

Examples of the acetophenone compounds include α -aminoketone compounds, α -hydroxyketone compounds and other acetophenone compounds.

Specific examples thereof include α -aminoketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one;

α -Hydroxyketone Compound α -aminoketone Compound is preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is particularly preferable.

Specific examples of the biimidazole compound are preferably 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole or 2,2 '-bis (2,4, 6-trichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, and particularly preferably 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole.

Examples of the acid generator include a photoacid generator and a thermal acid generator. Even a photoacid generator can be used as a thermal acid generator when an acid is generated by heating.

The acid generator includes an ionic compound and a nonionic compound, and preferably a nonionic compound. By using a nonionic generating agent, the light transmittance and the like of the obtained cured film can be improved.

The photoacid generator is a compound that generates an acid upon irradiation with light or other radiation. Examples of the radiation include: ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. By using the photoacid generator, cationic polymerization of the component (a) is generally caused in the radiation-sensitive resin composition by irradiation with radiation. Examples of the photoacid generator include: oxime sulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, onium salts, and the like. Among these, oxime sulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylate compounds are nonionic compounds. On the other hand, onium salts are ionic compounds.

The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (4).

[ solution 7]

In the formula (4), R^B1Is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

R^B1The alkyl group (C) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. R^B1The alkyl group (C) may be substituted with an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as 7, 7-dimethyl-2-oxonorbornyl group, etc., preferably a bicycloalkyl group, etc.). R^B1The aryl group(s) is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or naphthyl group. R^B1The aryl group of (A) may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom.

The oxime sulfonate compound represented by the above formula (4) is preferably an oxime sulfonate compound represented by the following formula (5).

[ solution 8]

In the formula (5), R^B1And R in the formula (4)^B1The same meanings are given. X is an alkyl group, an alkoxy group or a halogen atom. m is an integer of 0 to 3. When m is 2 or 3, plural X's may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group for X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. Particularly preferred is a compound of the formula (5) wherein m is 1, X is a methyl group, and the substitution position of X is an ortho position.

Specific examples of the oxime sulfonate compound include: and compounds (5-i), (5-ii), (5-iii), (5-iv) and (5-v) represented by the following formulae (5-i) to (5-v), respectively.

[ solution 9]

These compounds may be used alone or in combination of 2 or more, and can also be used in combination with other [ B ] acid generators. The compound (5-i) [ (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile ], the compound (5-ii) [ (5H-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile ], the compound (5-iii) [ (camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile ], the compound (5-iv) [ (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile ], and the compound (5-v) [ (5-octylsulfonyloxyimino) - (4-methoxyphenyl) ethylidene ] Nitrile ] is available as a commercial product.

Examples of the sulfonimide compound include: n- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N-methyl-phenylsulfonyloxy-N-phenylsulfonyloxy-phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, and the like.

Onium salts include: iodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazolium salts, tetrahydrothiophenium salts, and the like. An example of the iodonium salt is diphenyliodonium tetrafluoroborate. Examples of triphenylsulfonium salts include: triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, and the like.

Among these acid generators, nonionic acid generators are preferable, and oxime sulfonate compounds and sulfonimide compounds are more preferable.

In addition, even a specific example of the photoacid generator can be used as a thermal acid generator by heating without performing light irradiation.

(ii) polymerizable compound other than component (C) and (A)

In the present invention, as the component (C), a polymerizable compound other than the component (a) can be used. Examples of the polymerizable group contained in the polymerizable compound include: (meth) acryloyl, epoxy, oxetanyl, and vinyl. Among these, from the viewpoint of radical polymerizability, polymerizable compounds having a (meth) acryloyl group or vinyl group are preferable.

By containing the component (C), the hardness of the obtained cured film can be increased, and the adhesion of the cured film to the substrate can be improved.

Specific examples of the component (C) include the following compounds.

The component (C) is preferably a monofunctional, difunctional or trifunctional or higher (meth) acrylate, for example, in terms of good polymerizability and improvement in strength of the cured film formed. In addition, a compound having a vinyl group in a vinyl sulfide derivative, a (meth) acrylate derivative, a vinyl sulfoxide derivative, or a vinyl sulfone derivative can also be used. These compounds are preferable in that sensitivity is improved and storage stability of the curable composition can be maintained well.

Examples of the monofunctional (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate, omega-carboxy polycaprolactone mono (meth) acrylate, and the like. Commercially available products thereof include, for example, under the trade names: aronix (registered trademark) M-101, Aronix (Aronix) M-111, Aronix (Aronix) M-114, and Aronix (Aronix) M-5300 (manufactured by Toyo Seisaku-sho Co., Ltd.); kayarad (registered trademark) TC-110S, Kayarad (Kayarad) TC-120S (manufactured by Kayarad); a bisco (Viscoat)158, a bisco (Viscoat)2311 (above, manufactured by osaka organic chemical industry (stock)), and the like.

Examples of the difunctional (meth) acrylate include: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, and the like. Commercially available products thereof include, for example, under the trade names: aronix (registered trademark) M-210, Aronix (registered trademark) M-240, and Aronix (registered trademark) M-6200 (available from Toyo Seisaku-sho Co., Ltd.); cayrade (KAYARAD) (registered trademark) HDDA, cayrade (KAYARAD) HX-220, cayrade (KAYARAD) R-604 (above, manufactured by japan chemicals (stock)); costart (Viscoat)260, costart (Viscoat)312, costart (Viscoat)335HP (supra, manufactured by osaka organic chemical industry (japan)); and (d) Light Acrylate 1,9-NDA (available from Kyoeisha chemical Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate;

a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate;

a mixture of ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri (meth) acrylate, succinic acid-modified dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide isocyanurate (EO) -modified diacrylate and isocyanuric acid EO-modified triacrylate;

and polyfunctional urethane acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having 2 or more isocyanate groups with a compound having 1 or more hydroxyl groups and 3,4, or 5 (meth) acryloyloxy groups in the molecule.

Examples of the commercially available product of the trifunctional or higher (meth) acrylate include, for example, under the trade name: aronius (registered trademark) M-309, Aronius (Aronix) M-400, Aronius (Aronix) M-405, Aronix (Aronix) M-450, Aronix (Aronix) M-7100, Aronix (Aronix) M-8030, Aronix (Aronix) M-8060, and Aronix (Aronix) TO-1450 (manufactured by Toyo Seiyaku Co., Ltd.); KAYARAD (KAYARAD) (registered trademark) TMPTA, KAYARAD (KAYARAD) DPHA, KAYARAD (KAYARAD) DPCA-20, KAYARAD (KAYARAD) DPCA-30, KAYARAD (KAYARAD) DPCA-60, KAYARAD (KAYARAD) DPCA-120, KAYARAD (KAYARAD) DPEA-12 (above, manufactured by KAYARAD); examples of the "acrylic urethane" include: new Frontier (New Frontier) (registered trademark) R-1150 (manufactured by first Industrial pharmaceutical Co., Ltd.), Kayarad (registered trademark) DPHA-40H (manufactured by Nippon chemical Co., Ltd.), and the like.

Among these, particularly preferred are the compounds containing ω -carboxy polycaprolactone monoacrylate, 1, 9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate;

a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;

a mixture of tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate;

commercially available products of ethylene oxide-modified dipentaerythritol hexaacrylate, polyfunctional acrylic urethane compounds, succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate.

Further, the polymerizable compounds represented by the following (c-1), (c-2), (c-3) and (c-5) can also be used. (c-4) represents Methyl Phenyl Vinyl (MPV) (aromatic vinyl compound (manufactured by Sumitomo refining Co., Ltd.)).

[ solution 10]

It is also possible to use compounds having a vinyl group in the vinyl sulfide derivatives, (meth) acrylate derivatives, vinyl sulfoxide derivatives or vinyl sulfone derivatives. Specific examples of such compounds include: vinyl sulfides, phenyl vinyl sulfoxides, divinyl sulfones, phenyl vinyl sulfones, bis (vinylsulfonyl) methane, and the like. Such a compound is preferable in terms of sensitivity improvement and the ability to maintain the storage stability of the curable composition well.

The component (C) as described above may be used alone or in combination of 2 or more.

The amount of the component (C) in the curable composition of the present invention is preferably 30 to 250 parts by mass, and more preferably 50 to 200 parts by mass, based on 100 parts by mass of the compound (a). By setting the range, a cured film can be formed with high resolution without causing a problem of development residual, which is preferable.

Metal oxide with particle size less than 100nm

The metal oxide is contained to increase the optical refractive index of the obtained hardened material. The metal oxide particles are particles having a refractive index of 1.6 or more as measured by the method described in examples. The average particle diameter of the metal oxide particles is, for example, 1nm or more and 100nm or less. When the average particle diameter is outside the above range, the coatability, low moisture permeability of the obtained cured product, high refractivity, and the like may be affected. The metal oxide particles are not particularly limited as long as they can exhibit high refractivity, and include inorganic particles such as titanium atom-containing particles, zirconium atom-containing particles, niobium atom-containing particles, tin atom-containing particles, zinc atom-containing particles, aluminum atom-containing particles, silicon atom-containing particles, and magnesium atom-containing particles, and specifically, for example, oxide particles of these and the like can be listed. The core particle is more preferably a particle containing a titanium atom, a particle containing a zirconium atom, or a combination thereof, in terms of having a high refractive index. Further, as the core particle, a titanium oxide (titania) particle, a zirconium oxide (zirconia) particle, or a combination thereof is more preferable. The core particle may contain other elements as long as the effect of the present invention is not affected. In addition, the use of the dispersant can improve the dispersibility of the metal oxide particles. The dispersant may use phosphate acrylate, phosphate ester, etc., but is not limited thereto. The amount of the dispersant used is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the core particles. When the amount of the coupling agent used is less than the lower limit and exceeds the upper limit, the dispersibility of the particles may be lowered.

The average particle diameter of the metal oxide particles in the present specification is a value measured by a Brunauer-Emmett-Teller method (BET method) or a siers (Sears) method. When the particle diameter of the metal oxide particles having a small particle diameter such that the average particle diameter is 10nm or less is measured, the siels method is preferable.

For example, according to the BET method as an example of the average particle diameter, the average particle diameter of the metal oxide particles can be obtained by a nitrogen adsorption method using a BET formula (BET equation). The siels method, which is an example of the average particle size, is a method of determining the equivalent diameter of the irregularly-shaped particles by titrating 1.5g of SiO corresponding to the equivalent diameter from pH4 to pH 9 as described in "Analytical Chemistry" volume 28, pages 1981 to 1983 (1956)₂The amount of 0.1N-NaOH required for the colloidal silica was determined to obtain the specific surface area of the colloidal silica, and the equivalent diameter was calculated therefrom.

The average particle diameter of the metal oxide particles may be measured by a known method, and may be referred to a catalog value of a metal oxide particle manufacturer.

In the present invention, hollow particles can be used in addition to the metal oxide particles. The hollow particles include inorganic hollow particles and organic hollow particles. The hollow particles are not particularly limited as long as they have pores inside. By using such particles, the amount of light incident on the particles can be increased, and further, light from the particles can be efficiently diffused. Further, by using the particles, a film or the like excellent in bending resistance can be easily obtained.

The number of particles used in the present composition may be 1 or 2 or more.

The particles are preferably mixed with other organic components and kept in a uniformly dispersed state as a composition, and organic hollow particles are preferable in terms of easily obtaining a composition kept in a uniformly dispersed state. Further, the organic hollow particles are also preferable in that the degree of freedom of adjustment such as molecular design and synthesis is high by blending other constituent materials in the present composition. Further, the organic hollow particles having a high toluene-insoluble content (90 mass% or more) have the above-described characteristics because they have the same degree of hardness as the inorganic hollow particles, and are also excellent in void retention when subjected to deformation due to thermal stress or the like.

The inorganic hollow particles are not particularly limited, and include Al₂O₃、SiO₂、ZnO、ZrO₂、TiO₂Indium Tin Oxide (ITO), Arsenic Trioxide (ATO), SnO, CeO₂、CaCO₃And inorganic particles such as polyorganosiloxane compounds, and the like, and particles having at least a part of the surface thereof subjected to a surface treatment, particularly a hydrophobic treatment, are preferable in terms of having low hygroscopicity and excellent dispersibility in an organic solvent.

Such inorganic hollow particles may be commercially available ones or may be synthesized by a conventionally known method, for example, a method described in japanese patent No. 5078620.

The organic hollow particles are not particularly limited, and examples thereof include organic crosslinked particles such as acrylic particles and styrene particles. As such organic hollow particles, commercially available products can be used, or they can be synthesized by conventionally known methods, for example, the methods described in Japanese patent laid-open Nos. 62-127336, 01-315454, 04-126771, 2002-241448, 2007-112935 and 5439102. As the organic hollow particles, crosslinked hollow polymer particles obtained by the following method, specifically, the method described in japanese patent No. 4843850, are preferable in terms of obtaining particles having high light diffusibility and excellent organic solvent resistance and shape retention, obtaining the present composition having excellent long-term stability, and further easily obtaining a film having high luminous efficiency. Hollow particles described in WO2018-128144 can be used.

< other additional materials >

The curable composition of the present invention may contain an organic solvent, a sensitizer, a polymerization inhibitor, an antioxidant, a surfactant, and the like, as required. If necessary, a solvent may be used, but the curable composition can be used without using a solvent.

[ antioxidant ]

The antioxidant is a component that decomposes a radical generated by exposure or heating or a peroxide generated by oxidation, and prevents bond cleavage of polymer molecules. As a result, the obtained cured film can be prevented from being oxidized and deteriorated with the passage of time, and, for example, a decrease in luminance of the cured film can be suppressed.

Specific examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, thiol compounds, benzotriazole compounds, benzophenone compounds, hydroxylamine compounds, salicylate compounds, and triazine compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. The antioxidant used in the present embodiment preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of satisfying both the transmittance and the sensitivity of the coating film, preferable antioxidants include: a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant or a thiol-based antioxidant. Further, hindered phenol-based antioxidants, phosphorus-based antioxidants, and thiol-based antioxidants are more preferable.

Examples of the hindered phenol antioxidant include: 2, 4-bis [ (laurylthio) methyl ] -o-cresol, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl), 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), 2, 4-bis (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1,3, 5-triazine, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. Other oligomer type and polymer type compounds having a hindered phenol structure, and the like can also be used.

Examples of the phosphorus-based antioxidant include: tri (isodecyl) phosphite, tri (tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, distearyl pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol a pentaerythritol diphosphite, and the like. Other oligomer type and polymer type compounds having a phosphite structure, and the like can also be used.

Examples of the thiol antioxidant include: 2, 2-thio-diethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 4-bis [ (octylthio) methyl ] -o-cresol, 2, 4-bis [ (laurylthio) methyl ] -o-cresol and the like. Other oligomer type and polymer type compounds having a thioether structure, and the like can also be used.

The lower limit of the content of the antioxidant with respect to 100 parts by mass of the sum of the components of the compound (a) and the compound (B) is preferably 0.01 part by mass, and more preferably 0.1 part by mass. The upper limit of the content of the antioxidant is preferably 10 parts by mass, more preferably 8 parts by mass, and still more preferably 7 parts by mass. By setting the content of the antioxidant within the above range, it is possible to effectively suppress the oxidation degradation and the like of the obtained cured film with the passage of time. When 2 or more antioxidants are used, the content is the total amount.

[ surfactant ]

The surfactant that may be contained in the curable composition of the present embodiment may be added for the purpose of improving the coatability of the curable composition, reducing coating unevenness, and improving the developability of the radiation-irradiated portion. Examples of preferred surfactants include: a fluorine-based surfactant and a silicone-based surfactant.

Examples of the fluorine-based surfactant include: 1,1,2, 2-tetrafluorooctyl (1,1,2, 2-tetrafluoropropyl) ether, 1,2, 2-tetrafluorooctylhexyl ether, and the like.

Commercially available products of these fluorine-based surfactants include: afuto (Eftop) (registered trademark) EF301, Eftop (Eftop) EF303, and Eftop (Eftop) EF352 (manufactured by new autumn chemical industries); meijia method (Megafac) (registered trademark) F171, meijia method (Megafac) F172, meijia method (Megafac) F173 (manufactured by diey son (DIC) (stock)); florode (Fluorad) FC430, florode (Fluorad) FC431 (manufactured by sumitomo 3M); assaika (Asahi Guard) AG (registered trademark) 710 (manufactured by Asahi glass (stock)); sanforuron (Surflon) (registered trademark) S-382, Sanforon (Surflon) SC-101, Sanforon (Surflon) SC-102, Sanforon (Surflon) SC-103, Sanforon (Surflon) SC-104, Sanforon (Surflon) SC-105, and Sanforon (Surflon) SC-106 (manufactured by AGC Qingmei Chemicals (AGC SEIMI CHEMICAL) (Strand); FTX-218 (manufactured by Nieus (Neos) (Strand)), and the like.

Examples of silicone surfactants include those available under the trade name: SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH 8400 Freud (FLUID) (manufactured by Toray Dow Corning Silicone (Strand)); organosiloxane polymer KP341 (manufactured by shin-Etsu chemical industries), and the like.

When a surfactant is used as any other component, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the component (a). The application property of the curable composition of the present embodiment can be optimized by setting the amount of the surfactant to 0.01 to 10 parts by mass.

As the phosphate ester compound, there can be mentioned: a reaction product of a 2-hydroxyethyl methacrylate 6-caprolactone (hexalactone) addition polymer and phosphoric anhydride ("KAYAMER PM-21" manufactured by japan chemical corporation), an alkyl (C12, C14, C16, C18) acid phosphate ("JB-512" manufactured by north-town chemical industry corporation), and the like. Such a phosphate ester compound is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the component (A). By setting the amount of the phosphate compound to 0.01 to 10 parts by mass, the adhesion of the cured film obtained from the curable composition of the present embodiment to the substrate can be improved.

As the adhesion promoter, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxetanyl group and the like can be preferably used, and examples thereof include trimethoxysilylbenzoic acid, γ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

If necessary, an organic solvent may be used. The organic solvent may be used alone or in combination of 2 or more.

Examples of the organic solvent that can be used in the curable composition of the present embodiment include: an organic solvent which dissolves or disperses the other content components and does not react with the other content components.

Examples thereof include: alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and methyl 3-methoxypropionate; ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether and the like; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

The amount of the organic solvent used in the case of using the curable composition for organic EL is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, based on the total amount of the curable composition.

In the curable composition for imprints, it is preferably 50 to 400 parts by mass, more preferably 100 to 300 parts by mass, based on the total amount of the curable composition.

The curable composition of the present invention is a curable composition having a viscosity in the range of 3 mPas to 30 mPas at 25 ℃. The viscosity is a value measured at 23 ℃ with an E-type viscometer ("TVE 22L" manufactured by eastern mechanical industries) in accordance with Japanese Industrial Standard (JIS) K2283. By setting the viscosity to the above range, the ink jet coatability can be improved, and coating defects such as coating unevenness and dishing on the coated surface can be prevented. The viscosity can be adjusted by the molecular weight of the compound (a) and the compound (B) contained in the curable composition and the addition amount ratio, and is particularly preferably adjusted by the molecular weight of the compound (a). The above-mentioned viscosity range is also a range in which the viscosity does not easily increase with the passage of time, and is preferable in this respect.

In the case of the curable composition for imprinting, the viscosity range when a solvent is contained is in the range of 1 mPas to 1000 mPas at 25 ℃. By using the solvent in a viscosity range containing the solvent, excellent imprintability can be exhibited.

The method of forming a cured film according to the present embodiment is formed by the following steps.

[ Process (1) ]

In the step (1), a solution of the curable composition is applied to the surface of a substrate, and is prebaked as necessary to form a coating film. Examples of the substrate used in the step (1) include: glass substrates, silicon wafers, plastic substrates, and substrates having various inorganic films such as silicon nitride formed on the surfaces of these substrates. Examples of the plastic substrate include: and substrates containing, as a main component, plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide.

The curable composition can be applied by any suitable method such as spray coating, roll coating, spin coating (spin coat), slit die coating, bar coating, and ink jet coating. Among these coating methods, the inkjet coating method is preferred. The pre-baking conditions may vary depending on the kind and content of the components contained in the curable composition, and may be, for example, about 30 seconds to 10 minutes at 60 ℃ to 100 ℃. The lower limit of the average film thickness of the coating film after prebaking is preferably 0.1. mu.m. The upper limit is preferably 15 μm, more preferably 10 μm, and still more preferably 8 μm.

[ Process (2) ]

In the step (2), the coating film formed in the step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation in this case include: ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

The exposure wavelength is preferably 300nm to 450 nm. The light source may be a high-pressure mercury lamp or a light-emitting diode (LED). The exposure amount is preferably 100J/m, for example²Above and 100,000J/m²The following. Further, a pattern may be formed by an imprint method as needed.

[ Process (3) ]

The coating film may be hardened by heating and baking (post-baking) the coating film as necessary. In the step (3), the lower limit of the calcination temperature is preferably 80 ℃. On the other hand, the upper limit of the calcination temperature is preferably 250 ℃. The calcination time varies depending on the type of heating equipment, and may be, for example, 5 minutes to 40 minutes when the heating treatment is performed on a hot plate, or 30 minutes to 80 minutes when the heating treatment is performed in an oven.

According to the production method, a cured film can be formed by radiation-sensitive exposure and heating using the curable composition.

< hard coating >

The refractive index of a cured product obtained by curing the curable composition of the present invention is 1.60 or more, preferably 1.65 or more. By using a medium element such as a sulfur atom or increasing the content of a condensed hydrocarbon ring, a cured product having a high refractive index can be designed. The cured film of the present invention can also be used for sealing of an organic EL element, a microlens, an antireflection film, a diffraction grating of an Augmented Reality (AR) element, and the like. Further, since the imprint material is excellent in etching resistance, high refractive index, and fluidity, it is useful for resists for producing wire grid polarizing plates, diffraction gratings for AR elements, and the like.