KR20170015904A - Photocurable resin composition - Google Patents

Abstract

Provided is a photocurable resin composition having high refractive index and high transparency and having a short fixing time. (Meth) acrylate having an alicyclic hydrocarbon group as the component (B), a monofunctional (meth) acrylate having one aromatic ring as the component (C), (meth) (A) is contained in an amount of 10 to 70 parts by mass and the content of the component (B) in a total amount of 100 parts by mass of the components (A) to (C) Is 5 to 65 parts by mass, and the content of the component (C) is 5 to 65 parts by mass.

Description

Photocurable resin composition [0002]

The present invention relates to a photo-curable resin composition.

Conventionally, on the surfaces of glass, film and sheet used for a sensor element such as a CCD or a CMOS or a display element such as a display, a coating layer made of an inorganic substance or an organic substance is provided for protecting the surface. In recent years, a coating layer in which a high refractive index layer and a low refractive index layer are alternately laminated is used for the purpose of imparting functions such as antireflection and optical wave to the surface protective layer. The high refractive index layer is formed by mixing a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia and alumina or a radical polymerizable monomer such as bisphenol A epoxy (meth) acrylate or urethane (meth) A high refractive index organic film which is irradiated with energy rays such as ultraviolet rays to form a cured film has been used according to purposes. In the case of the former inorganic film, when the base material is a film or a sheet, there is a problem such that the film is liable to be insufficiently adhered or the film is easily broken. In recent years, a photo-curable high refractive index organic film containing a radical polymerizable monomer has been widely used.

In assembling optical devices such as a camera or a microscope, a transparent resin such as balsam or epoxy resin is used as an adhesive in order to bond a lens or a prism. BACKGROUND ART [0002] With the development of the optoelectronics industry in recent years, applications for bonding optical elements having high optical functions such as optical fibers and microlenses have been increasing. Adhesives blended with radical polymerizable monomers such as bisphenol A type epoxy (meth) acrylate or urethane (meth) acrylate have been widely used for bonding optical elements. Particularly, when an optical circuit such as an optical modulator or an optical switch is manufactured by joining an optical waveguide element and a microlens or an optical fiber or an optical component requiring a high optical characteristic such as bonding of a thin lens is bonded An adhesive having a high refractive index is required.

As a resin composition for use in a resin composition or an adhesive having a high refractive index applicable to the high refractive index layer used in the antireflection film or optical waveguide film as described above, an adhesive composition using a sulfur-containing (meth) acrylate and a photo- (Patent Literatures 1 to 3). Patent Document 4 discloses an active energy ray curable composition using a urethane (meth) acrylate having a diphenyl sulfone structure.

Further, a photo-curable resin composition using (meth) acrylate having a fluorene skeleton as a compound having a high refractive index has been disclosed (Patent Documents 5 to 9).

Further, Patent Documents 5 to 9 disclose that monofunctional (meth) acrylate can be used for the purpose of dilution or the like.

Patent Document 1: JP-A-11-5952 Patent Document 2: JP-A-2002-97224 Patent Document 3: Japanese Published Patent Application No. 2006-526037 Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-157543 Patent Document 5: JP-A-2004-294720 Patent Document 6: JP-A-2008-94987 Patent Document 7: JP-A-2010-248358 Patent Document 8: Japanese Laid-Open Patent Publication No. 2011-39165 Patent Document 9: Japanese Unexamined Patent Application Publication No. 2012-111931

However, urethane (meth) acrylate and 4,4'-dimercapto diphenyl sulfide dimethacrylate having a sulfur-containing (meth) acrylate or diphenyl sulfone structure as main components described in Patent Documents 1 to 4 are bisphenol A (Meth) acrylate. However, since these compounds generally absorb light having a wavelength of 450 nm or less, they are colored in yellow, so transparency tends to be lowered, and it is difficult to adhere to the film There was a problem of.

On the other hand, the embodiment of Patent Document 5 uses dimethacrylate having an ethylene glycol chain and / or bisphenol F ethylene oxide modified acrylate as a component other than (meth) acrylate having a fluorene skeleton, And the like.

In the example of Patent Document 6, since a monofunctional (meth) acrylate compound having two aromatic rings is used as a component other than the (meth) acrylate having a fluorene skeleton, a high refractive index was obtained, but the adhesiveness, transparency, And the like.

The embodiment of Patent Document 7 is a method for producing a fluoroelastomer having a monofunctional (meth) acrylate having two aromatic rings as a component other than the (meth) acrylate having a fluorene skeleton and / or a monofunctional (meth) acrylate having one aromatic ring A high refractive index was obtained, but there were problems such as adhesion, transparency, and low light resistance.

Since the embodiment of Patent Document 8 uses an alkali-soluble resin and a silica fine particle as the (meth) acrylate copolymer having a carboxyl group and an ethylenic unsaturated group in the molecule as a component other than the (meth) acrylate having a fluorene skeleton, And the like.

In the example of Patent Document 9, since a multifunctional curable monomer having three or more (meth) acryloyl groups in the molecule is used as a component other than (meth) acrylate having a fluorene skeleton, adhesion, There was a problem of.

Patent Documents 5 to 9 do not describe the composition ratio of monofunctional (meth) acrylate.

The present invention has been made in view of such circumstances. The present invention uses a specific amount of monofunctional (meth) acrylate. According to the present invention, it is possible to use dimethacrylate having an ethylene glycol chain described in Patent Documents 5 to 9, bisphenol F ethylene oxide modified acrylate, monofunctional (meth) acrylate having two aromatic rings, carboxyl group and ethylenically unsaturated (Meth) acrylate copolymer and silica fine particles and a polyfunctional curable monomer having three or more (meth) acryloyl groups in the molecule are not used. The present invention provides a photocurable resin composition having a high refractive index and high transparency and having a short fixing time.

The present invention is as follows.

<1> A fluorene-based compound represented by the following general formula (1) as the component (A)

(2)

(In the general formula (1), R ¹ , R ² , R ³ and R ^{4 each} represent a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4. Each substituent may be a substitutable Carbon atom.)

(Meth) acrylate having an alicyclic hydrocarbon group as the component (B)

(Meth) acrylate having one aromatic ring as the component (C)

(D) as a photo radical polymerization initiator

, The content of the component (A) is 10 to 70 parts by mass, the content of the component (B) is 5 to 65 parts by mass, the content of the component (A) is 100 parts by mass, And the content of the component (C) is 5 to 65 parts by mass.

&Lt; 2 > The component (B) preferably has a homopolymer having a glass transition temperature of not lower than 40 DEG C but not higher than 180 DEG C.

<3> It is preferable that a component (E) further contains a silane coupling agent.

<4> The component (E) is preferably a silane coupling agent having at least one functional group selected from a phenyl group or a (meth) acryloyl group.

&Lt; 5 > It is preferable that the liquid refractive index at a temperature of 25 DEG C and a wavelength of 589 nm is 1.50 or more, and a cured product refractive index is 1.53 or more.

&Lt; 6 > A cover material made of a photo-curable resin composition is preferable.

<7> Preferably, the base material has a covering material.

<8> It is preferable that the film is formed by forming a layer made of a photo-curing resin composition on a substrate and then forming a layer having a refractive index lower than that of the photo-curable resin composition.

It is preferable that the base material has a film.

<10> It is preferable that the element has a base material.

<11> It is preferable that the adhesive is composed of a photocurable resin composition.

<12> It is preferable that the bonded body is bonded with an adhesive.

<13> An optical component having a junction body is preferable.

The present inventors have conducted research and development of a photo-curing resin composition using the fluorene compound represented by the above general formula (1). As a result, the photo-curable resin composition of the fluorene compound was prepared using the monofunctional (meth) acrylate used for the purpose of dilution or the like. As a result, the photo-curing resin composition having a higher refractive index, higher transparency, A composition was obtained. As a result of further studies, it has been found that by mixing a monofunctional (meth) acrylate having an alicyclic hydrocarbon group and a monofunctional (meth) acrylate having one aromatic ring at a specified content ratio, The present inventors have completed the present invention.

The present invention can provide effects such as high refractive index, high transparency, and short fixing time.

<Explanation of Terms>

In the present specification, the covering material means a material which covers the surface of a base material such as a glass substrate, a plastic film, or a plastic sheet for the purpose of imparting surface protection or designability, or imparting functions such as antireflection and optical wave.

In the present specification, the term &quot; adhesive &quot; means an adhesive for sticking parts and components, particularly, an adhesive suitably used for bonding optical components.

The components of the resin composition according to one embodiment of the present invention will be described. The total amount of the components (A) to (C) in 100 parts by mass of the photocurable resin composition of the present embodiment is preferably 70 parts by mass or more, more preferably 90 parts by mass or more, and more preferably 93 parts by mass or more And still more preferably 95 parts by mass or more. The total amount of the components (A) to (C) in the 100 parts by mass of the photocurable resin composition is 60, 65, 70, 75, 80, 85, 88, 90, 92, 93 , 95, 96, 97, 98, 99, or 100 parts by mass, and may be within the range of any two of these values.

&Lt; Component (A): Fluorene compound >

The resin composition of the present embodiment has a fluorene-based compound represented by the following general formula (1) as the component (A).

(3)

(In the general formula (1), R ¹ , R ² , R ³ and R ^{4 each} represent a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4. Each substituent may be a substitutable Carbon atom.)

Examples of the fluorene compound include 9,9-bis [(meth) acryloyloxyphenyl] fluorenes such as 9,9-bis [4 - ((meth) acryloyloxy) phenyl] fluorene; Phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [((meth) acryloyloxy C 2-4 alkoxy) phenyl] fluorenes such as omega; (3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [ Bis [mono (meth) acrylate] such as 9,9-bis [3,5-dimethyl- Or diC1-4alkyl- (2- (meth) acryloyloxyC2-4alkoxy) phenyl] fluorene; Di [2- (meth) acryloyloxyethoxy] phenyl] fluorene, 9,9-bis [ Di (2- (meth) acryloyloxyC2-4alkoxy) phenyl] fluorenes such as ethoxy) phenyl] fluorene; (Meth) acryloyloxy C2 (meth) acrylate such as 9,9-bis [3,4,5-tris (2- (meth) acryloyloxyethoxy) -4-alkoxy) phenyl] fluorenes; (9,9-bis [(meth) acryloyloxy C 2-4 alkoxy) phenyl] fluorene in which a C 2-4 alkoxy group is substituted with a polyalkoxy group (diethoxy, triethoxy group, etc.) Ryu; 9,9-bis [3,5-dimethyl-4- (2- ((meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, (Meth) acryloyloxy C 2-4 alkoxy C 2-4 alkoxy) phenyl] fluorenes such as 2- (meth) acryloyloxyethoxy) ethoxy) phenyl] ); Further, in these compounds, the compound (9,9-bis [3-phenyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene 9,9-bis [phenyl- (meth) acryloyloxy C2-4 alkoxyphenyl] fluorenes, etc.); In these compounds, a compound which is a naphthyl group (9,9-bis [5 or 6- (2- (meth) acryloyloxyethoxy) -2-naphthyl)] fluorene, 9,9- (Meth) acryloyloxy C 2-4 alkoxy) naphthyl such as 6- (2- (meth) acryloyloxyethoxy) -1 or 2-naphthyl) ] Fluorenes) and the like. Among these, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and / or 9,9-bis [4- 2- (meth) acryloyloxypolyethoxy) phenyl] fluorene are preferable. Here, C is carbon. For example, C1-4 means C1-4 carbon atoms.

The content of the component (A) is preferably from 10 to 70 parts by mass, more preferably from 20 to 60 parts by mass per 100 parts by mass of the total amount of the resin composition (from 100 parts by mass of the total of the components (A) to (C)) from the viewpoints of refractive index, transparency, And most preferably 30 to 50 parts by mass. The content of the component (A) may be, for example, 10, 20, 30, 40, 50, 60 or 70 parts by mass, and may be in the range of any two values.

As the fluorene compound, those prepared by a known production method may be used. Specifically, it is possible to use "ozol series" manufactured by Osaka Gas Chemical Co., Ltd. and "NK Ester A-BPFE" manufactured by Shin Nakamura Chemical Industries Co.,

&Lt; Component (B): (meth) acrylate having an alicyclic hydrocarbon group >

The resin composition of this embodiment contains a monofunctional (meth) acrylate having an alicyclic hydrocarbon group as the component (B).

Examples of the monofunctional (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) Acrylate, cyclohexyl (meth) acrylate, hydrogenated bisphenol A (meth) acrylate, isobornyl (meth) acrylate, (Ethylene oxide) modified product of these epoxy mono (meth) acrylates, hydrogenated bisphenol F type epoxy mono (meth) acrylate, hydrogenated biphenyl type epoxy mono (meth) acrylate, and epoxy mono Or a PO (propylene oxide) modified product. Among them, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like are preferable from the viewpoints of refractive index, transparency, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate, and is preferably at least one selected from the group consisting of isobonyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate.

(B) preferably has a glass transition temperature (hereinafter referred to as Tg) of from 40 캜 to 180 캜 in terms of adhesion and light resistance.

The glass transition temperature (Tg) of the homopolymer of (meth) acrylate is determined by the method described in J. Brandrup, EHImmergut, Polymer Handbook, 2nd Ed., J. Wiley, New York 1975, . In this embodiment, the values described in the photocuring technology data book are used.

The glass transition temperature can be measured by a known method such as differential calorimetry (hereinafter referred to as DSC) or dynamic viscoelasticity (hereinafter referred to as DMA), but measurement using DSC is preferable.

The content of the component (B) is preferably from 5 to 65 parts by mass, more preferably from 15 to 60 parts by mass based on the total amount of the resin composition (100 parts by mass in total of the components (A) to (C)) from the viewpoints of refractive index, transparency, More preferably 55 parts by mass, and most preferably 25 to 45 parts by mass. The content of the component (B) may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65 parts by mass, .

<Component (C): monofunctional (meth) acrylate having an aromatic ring>

The resin composition of the present embodiment contains a monofunctional (meth) acrylate having one aromatic ring for the purpose of further increasing the refractive index as the component (C).

Examples of the monofunctional (meth) acrylate having one aromatic ring include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (Meth) acrylate, nonylphenyl (meth) acrylate, ethylene oxide-modified nonylphenyl (meth) acrylate, phthalic acid-modified (meth) acrylate and the like. Among these, benzyl (meth) acrylate and / or phenoxyethyl (meth) acrylate are preferable from the viewpoint of compatibility with component (A), refractive index and transparency.

The content of the component (C) is preferably 5 to 65 parts by mass, more preferably 10 to 55 parts by mass with respect to the total amount (100 parts by mass in total of the components (A) to (C)) of the resin composition in terms of refractive index, transparency, More preferably 15 to 45 parts by mass, and most preferably 15 to 45 parts by mass. The content of the component (C) may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65 parts by mass, .

&Lt; Component (D): photo radical polymerization initiator >

The resin composition of the present embodiment contains (D) a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited as long as it is a compound which generates a radical by irradiation of an energy ray.

Examples of the photo radical polymerization initiator include benzoin derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone derivatives such as benzophenone and 4-phenylbenzophenone , Alkyl acetophenone derivatives such as 2,2-diethoxyacetophenone and benzyl dimethyl ketal, ketone derivatives such as 1-hydroxy-cyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2- Aminoalkyl acetophenone derivatives such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1, isobutyryl-methylphosphinic acid methyl ester, isobutyryl- Fins acid methyl ester , Pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoylphenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-tolyl-phenylphosphinic acid methyl ester, o-tolyl- P-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, pivaloyl- (4-methylphenyl) -phosphinic acid methyl ester, pivaloylphenylphosphinic acid methyl ester, Phenylphosphinic acid methyl ester, isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-1-cyclohexanoyl-diphenyl Tert-butylbenzoyl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, o-tolyl-diphenylphosphine oxide, , (Meth) acryloyldiphenylphosphine oxide, benzo Diphenylphosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, 2,6- Benzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphosphine oxide, 2,4 , 6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl 2-methylbenzoyl-phenylphosphinic acid ester, 2,6-dichlorobenzoyl-diphenylphosphinic acid, 2, 6-dichlorobenzoyl-diphenylphosphinic acid ester, , 3,4,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,6-dimethyl 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl- or 2,6-dimethoxy Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis Acylphosphine oxide derivative, 1,2- octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone 1- [ Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). Of these, at least one selected from the group consisting of alkyl acetophenone derivatives,? -Hydroxyacetophenone derivatives and acylphosphine oxide derivatives is preferable in view of excellent reactivity and transparency. These may be used alone or in combination of two or more.

The content of the component (D) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the total amount of the resin composition (100 parts by mass in total of (A) to (C)). When the amount is in the range of 0.1 to 10 parts by mass, the curability does not deteriorate and the transparency does not deteriorate either. The content of the component (D) may be, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by mass, It can be inside.

&Lt; Component (E): Silane coupling agent >

As one embodiment of the present invention, the resin composition may further contain a silane coupling agent as the component (E) for the purpose of further improving the adhesion to the glass surface. Examples of the silane coupling include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? -Methacryloxypropyltri Methacryloxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Mercaptopropyltri Aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? -Ureido propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, and the like. Among these, at least one member selected from the group consisting of a silane coupling agent having a (meth) acryloyl group, a silane coupling agent having an epoxy group, and a silane coupling agent having a phenyl group is preferable, and a silane coupling agent having a (meth) acryloyl group And a silane coupling agent having a phenyl group are more preferable. Examples of the silane coupling agent having a (meth) acryloyl group include? -Methacryloyloxypropyltrimethoxysilane and? -Acryloyloxypropyltrimethoxysilane. Examples of the silane coupling agent having an epoxy group include? -Glycidoxypropyltrimethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Examples of the silane coupling agent having a phenyl group include phenyltrimethoxysilane and phenyltriethoxysilane.

The content of the component (E) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass per 100 parts by mass of the total amount of the resin composition (100 parts by mass in total of the components (A) to (C)) from the viewpoints of refractive index, transparency, desirable. The content of the component (E) may be, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by mass, It can be inside.

The resin composition of the present embodiment may contain a monofunctional (meth) acrylate compound or a polyfunctional (meth) acrylate other than the above in addition to the effects of the present embodiment.

<Other additives>

Various additives such as an antioxidant, an acrylic rubber, a urethane rubber, etc., a photosensitizer, a light stabilizer, a solvent, an increasing agent, a filler, a reinforcing agent, a plasticizer, a thickener, a dye, a pigment, An additive such as a surfactant may be contained.

The method for producing the resin composition according to the present embodiment is not particularly limited as long as the above materials can be sufficiently mixed. The method of mixing the materials is not particularly limited, and examples thereof include a stirring method using an agitating force in accordance with the rotation of the propeller, and a method using a conventional dispersing machine such as a planetary stirrer by rotating revolution. These mixing methods are preferable because stable mixing can be performed at a low cost.

After the above mixing, the resin composition can be cured by irradiation of energy rays using the following light source.

In the present embodiment, the light source used for curing the resin composition is not particularly limited, but a halogen lamp, a metal halide lamp, a high power metal halide lamp (including indium), a low pressure mercury lamp, a high pressure mercury lamp, A lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and a light-emitter diode (hereinafter referred to as an LED). These light sources are preferable in that irradiation of energy rays corresponding to the reaction wavelength of each photo radical polymerization initiator is efficiently performed.

The light sources have different emission wavelengths and energy distributions, respectively. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator and the like. Natural light (sunlight) can also be a reaction-initiating light source.

The light source may be subjected to direct irradiation, light irradiation with a reflector or the like, or light irradiation with a fiber or the like. A low-wavelength cut filter, a hot-wire cut filter, a cold mirror, or the like may also be used.

The resin composition having the above-described constitution can be rapidly cured by irradiation with energy rays, and thus can provide a cured product having excellent optical properties such as high transparency and high refractive index.

In one embodiment of the present invention, the refractive index of the resin composition is preferably 1.50 or more, more preferably 1.51 or more, and most preferably 1.52 or more, at a temperature of 25 DEG C and a wavelength of 589 nm.

In one embodiment of the present invention, the refractive index of the resin composition is preferably 1.53 or more, more preferably 1.54 or more, and most preferably 1.55 or more, at a temperature of 25 DEG C and a wavelength of 589 nm.

The refractive index can be measured by a known method such as Abbe's refractometer, prism coupler, and ellipsometer. Of these, measurement using an Abbe's type refractive index meter is preferable.

The resin composition having the above composition is excellent in optical properties such as high transparency and high refractive index and is excellent in adhesion to base materials such as glass, plastic film and plastic sheet, and thus can be provided as a covering material for these base materials.

The resin composition having the above structure can be used as a high refractive index layer of an antireflection film or a waveguide film because of its excellent optical properties such as high transparency and high refractive index. Therefore, the resin composition having the above-described constitution can provide an excellent antireflection film or optical waveguide film.

The antireflection film and the optical waveguide film are formed by applying a layer made of the resin composition of the present embodiment (hereinafter referred to as a high refractive index layer) on various base materials such as glass, plastic film and plastic sheet, curing the film by energy ray irradiation, (Hereinafter referred to as a low refractive index layer) on the high refractive index layer with a refractive index lower than that of the high refractive index layer.

Examples of the base material include glass base materials such as alkali-free glass, alkali glass, borosilicate glass and quartz, ceramic base materials such as silica, alumina and silicon nitride, metal base materials such as silicon, aluminum, stainless steel, iron, copper and silver, , A film base material made of a resin such as a styrene resin, a carbonate resin, an olefin resin, a polyester resin, a polyimide resin, a polyamide resin, an epoxy resin, a silicone resin, a fluorine resin, A sheet base material or the like can be used.

The low refractive index layer may be an inorganic film or an organic film. Examples of the inorganic film include fluorides of alkali metals such as magnesium fluoride and potassium fluoride, and silica. Examples of the organic film include fluorine resins such as polyperfluoroethylene and perfluorocycloolefin; polyether resins such as polyethylene glycol; silicone resins; acrylic resins; epoxy resins; urethane resins; and fluorine-modified resins thereof.

Since the resin composition having the above composition is excellent in optical characteristics such as high transparency and high refractive index, it can be used as a display element of a liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smart phone, , CMOS, and biochip, coating materials for semiconductor devices such as flash memory, DRAM, and semiconductor lasers, and further as a high refractive index layer of antireflection film or optical waveguide film.

The resin composition having the above-described constitution has a high refractive index and high transparency, and therefore, it is possible to provide an adhesive suitable for bonding an optical component.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited thereto.

The following compounds were used in the Examples.

(A) a fluorene compound

(BPFEA) manufactured by Osaka Gas Chemical Co., Ltd.) (A-1) 9,9-Bis [4- (2- acryloyloxyethoxy) phenyl] fluorene

(A-2) 9,9-bis [4- (2-acryloyloxydiethoxy) phenyl] fluorene ("Oak Sol EA-0200" manufactured by Osaka Gas Chemical Co.,

(B) a (meth) acrylate having an alicyclic hydrocarbon group

(B-1) dicyclopentenyloxyethyl methacrylate ("Pancryl FA-512M" manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 46 ° C)

(B-2) cyclohexyl methacrylate ("Light Ester CH" manufactured by Kyowa Chemical Industry Co., Ltd., homopolymer Tg: 66 ° C)

(B-3) isobornyl acrylate ("Light Acrylate IB-XA" manufactured by Kyowa Chemical Co., Ltd., homopolymer Tg: 94 ° C)

(B-4) dicyclopentenyl acrylate ("Pancryl FA-511AS" manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 120 ° C)

(B-5) 2-methyl-2-adamantyl methacrylate ("Adamantate MM" manufactured by Idemitsu Kosan Co., Ltd., homopolymer Tg: 170 ° C)

(B-6) dicyclopentyl methacrylate ("Pancryl FA-513M" manufactured by Hitachi Chemical Co., Ltd., homopolymer Tg: 175 ° C)

(B-7) isobornyl methacrylate ("Light Ester IB-X" manufactured by Kyowa Chemical Industry Co., Ltd., homopolymer Tg: 180 ° C.)

(C) a monofunctional (meth) acrylate having an aromatic ring

(C-1) phenoxyethyl acrylate ("Light Acrylate PO-A" manufactured by Kyowa Chemical Industry Co., Ltd.)

(C-2) Phenoxyethyl methacrylate ("LIGHT ESTER PO" manufactured by Kyowa Chemical Industry Co., Ltd.)

(C-3) benzyl acrylate ("Viscot # 160" manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(C-4) benzyl methacrylate (&quot; Lite Ester BZ &quot; manufactured by Kyowa Chemical Industry Co., Ltd.)

(D) a photo radical polymerization initiator

(D-1) 1-Hydroxy-cyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF)

(D-2) bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure 819" manufactured by BASF)

(D-3) benzyl dimethyl ketal ("Irgacure 651" manufactured by BASF)

(E) Silane coupling agent

(E-1)? -Methacryloyloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Silicone Co., Ltd.)

(E-2) phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Silicone Co., Ltd.)

(E-3) phenyltriethoxysilane (KBE-103 manufactured by Shin-Etsu Silicone Co., Ltd.)

As comparative examples, the following (meth) acrylates not corresponding to the above (B) and (C) were used.

(F-1) 2-ethylhexyl methacrylate ("Light Ester EH" manufactured by Kyowa Chemical Industry Co., Ltd., homopolymer Tg: -10 ° C)

(F-2) bisphenol A ethylene oxide-modified diacrylate (ARONIX M-211B manufactured by Toa Synthesis Co., Ltd.)

(F-3) bisphenol F ethylene oxide-modified diacrylate (Aronix M-208 manufactured by Toa Synthesis Co., Ltd.)

(F-4) Ethylene glycol dimethacrylate ("NK ester 1G" manufactured by Shin-Nakamura Chemical Co., Ltd.)

(F-5) 2- (ο-phenylphenoxy) ethyl acrylate ("NK Ester A-LEN-10" manufactured by Shin-Nakamura Chemical Co., Ltd.)

(Examples 1 to 30 and Comparative Examples 1 to 10)

The raw materials of the kinds shown in Tables 1 to 4 were mixed in the content ratios (units: parts by mass) shown in Tables 1 to 4 to prepare resin compositions for coating materials and evaluation described later. The various evaluation results are shown in Tables 1 to 4. Unless otherwise specified, was conducted in an environment of 23 ° C and a humidity of 50%.

〔Assessment Methods〕

〔Viscosity〕

The viscosity at 25 ° C was measured using an E-type viscometer.

[Fixing time]

Heat-resistant glass (trade name "Heat-resistant Pyrex (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) was used. The adhesive was applied to one heat-resistant glass with a film thickness of 30 m, and then the other heat-resistant glass was overlapped. A load of 4 kg was applied to the heat-resistant glass while irradiating ultraviolet rays under the condition of an irradiation intensity of 30 mW / cm 2 at a wavelength of 365 nm in an ultra-high pressure mercury lamp mounted device ("UL-750" The time from when the ultraviolet ray was irradiated until the heat-resistant glass can not move even when the load is applied is measured.

[Evaluation of refractive index]

(1) liquid refractive index

The refractive index of the liquid was measured at a temperature of 25 DEG C and a wavelength of 589 nm by using a multi-wavelength Abbe's refractometer ("DR-M2" manufactured by ATAGO Co., Ltd.).

(2) Cured product refractive index

The adhesive composition was poured into a mold made of silicone rubber having a volume of 15 mm x 15 mm x 1.0 mm. A cured product specimen was cured under the conditions of an irradiation intensity of 30 mW / cm 2 and a cumulative light quantity of 3,000 mJ / cm 2 at a wavelength of 365 nm in an ultrahigh-pressure mercury lamp mounting apparatus ("UL-750" manufactured by HOYA Corporation) and the refractive index was evaluated. The refractive index was measured at a temperature of 25 DEG C and a wavelength of 589 nm using a multi-wavelength Abbe's refractometer ("AT-M2" manufactured by Atagosa Co., Ltd.).

[Evaluation of spectral transmittance]

The resin composition was coated on a heat-resistant glass (trade name: "Heat-resistant Pyrex (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) to a film thickness of 30 μm and then exposed to ultraviolet light at 365 nm And a total intensity of 3,000 mJ / cm &lt; 2 &gt;. Using a UV-visible spectrophotometer ("UV-2550" manufactured by Shimadzu Corporation), the transmittance of 400 nm was measured using heat-resistant glass as a reference.

[Evaluation of adhesion (cross-cut test)]

High-pressure mercury lamp mounting device (UL-750 manufactured by HOYA Corporation) was irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation intensity of 30 mW / cm 2 and a cumulative light quantity of 3,000 mJ / cm 2 on a 125 μm thick polyester film (Cosmo Shine A4100, , And the resin composition was cured under a nitrogen atmosphere to prepare a test piece having a cured film of a resin composition of 20 mm x 20 mm x 80 m in shape.

Each of the thus-obtained test pieces was subjected to a cut line so as to have a length of 2 mm x 2 mm x 25 mm in a cured film under an environment of a temperature of 23 캜 and a relative humidity of 50%. A cellophane tape (Nichirei Reflective Model CT-405AP: , Adhesive force of 23 N / 10 mm) was attached to the plate to perform 180 ° peeling. The number of the remaining masses after 180 ° peeling was counted and evaluated. Other conditions not otherwise specified are in accordance with JIS K 5600-5-6.

[Evaluation of tensile shear bond strength]

The resin composition was applied to a circular shape having a diameter of 8 mm on a heat-resistant glass (trade name: "Heat-resistant Pyrex (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) at a thickness of 80 μm and then mounted on a super high pressure mercury lamp mounting device -750 &quot;) with a wavelength of 365 nm at an irradiation intensity of 30 mW / cm &lt; 2 &gt; and an accumulated light quantity of 3,000 mJ / cm & The tensile shear bond strength was measured at a tensile speed of 10 mm / min using a tensile tester in an environment of 23 ° C and a humidity of 50% RH.

[Evaluation of light resistance (light fastness test)]

The resin composition was coated on a heat-resistant glass (product name: "Heat-resistant Pyrex (registered trademark)", 25 mm × 25 mm × 2.0 mm) with a film thickness of 30 μm and then exposed to ultraviolet light at 365 nm And a total intensity of 3,000 mJ / cm &lt; 2 &gt;. The resin side of the test piece, which had been made into a light having an illuminance of 50 W / m &lt; 2 &gt;, was continuously irradiated for 100 hours using a light resistance tester (Xenon Weatherometer X75, product of Suga Test Instruments Co., Ltd.). The transmittance of the specimen after irradiation was measured at 400 nm using an ultraviolet-visible spectrophotometer ("UV-2550" manufactured by Shimadzu Corporation). Heat-resistant glass was used as a reference.

The resin compositions of Experimental Examples 1 to 30 had high refractive index and high transparency, had a short fixation time, and were excellent in adhesion and light resistance. Further, such a composition before curing had excellent workability because it had a low viscosity. Furthermore, the resin composition obtained by using the monofunctional (meth) acrylate having two aromatic rings in place of the component (C) in comparison with the resin compositions of Experimental Examples 1 to 30 showed high viscosity and low transmittance, adhesion and adhesive strength ( Comparative Example 10).

INDUSTRIAL APPLICABILITY The present invention has high refractive index and high transparency, has a short fixing time, and is excellent in adhesion and light resistance. The present invention has low viscosity and excellent workability.

INDUSTRIAL APPLICABILITY The present invention is applicable to various sensor elements, display elements, optical components and the like. INDUSTRIAL APPLICABILITY The present invention is used for a surface protection of a sensor element, a display element and the like, an antireflection film, an optical waveguide film and an adhesive of an optical component. The present invention is applied to a high refractive index layer of an antireflection film or an optical waveguide film. INDUSTRIAL APPLICABILITY The present invention is applied to an adhesive composition for optical parts used for bonding optical elements such as optical lenses, prisms, and optical waveguides.

Since the resin composition of the present invention has excellent optical properties such as high transparency and high refractive index, it can be used as a display element such as a liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smart phone, a mobile phone, a digital camera, A cover material used for a semiconductor device such as a flash memory, a DRAM, and a semiconductor laser, and further, as a high refractive index layer of an antireflection film or a waveguide film. Since the resin composition of the present invention is excellent in adhesion and light resistance, it can be suitably used as an adhesive for optical parts. The present invention is very useful in industry.

Claims (13)

As the component (A), a fluorene-based compound represented by the following general formula (1)
[Chemical Formula 1]

(In the general formula (1), R ¹ , R ² , R ³ and R ^{4 each} represent a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4. Each substituent may be a substitutable Carbon atom.)
(Meth) acrylate having an alicyclic hydrocarbon group as the component (B)
(Meth) acrylate having one aromatic ring as the component (C)
(D) as a photo radical polymerization initiator
, The content of the component (A) is 10 to 70 parts by mass, the content of the component (B) is 5 to 65 parts by mass, the content of the component (A) is 100 parts by mass, Wherein the content of the component (C) is 5 to 65 parts by mass. The method according to claim 1,
(B) is a homopolymer having a glass transition temperature of not less than 40 ° C and not more than 180 ° C. The method according to claim 1 or 2,
And a silane coupling agent as a component (E). The method of claim 3,
(E) is a silane coupling agent having at least one functional group selected from a phenyl group or a (meth) acryloyl group. The method according to any one of claims 1 to 4,
A liquid refractive index at a temperature of 25 DEG C and a wavelength of 589 nm of 1.50 or more, and a cured product refractive index of 1.53 or more. A covering material comprising the photocurable resin composition according to any one of claims 1 to 5. A base material having the coating material according to claim 6. A film formed by forming a layer made of the photo-curable resin composition according to any one of claims 1 to 5 on a substrate and then forming a layer having a refractive index lower than that of the photo-curable resin composition. A base material having the film according to claim 8. An element having the base material according to claim 9. An adhesive comprising the photo-curable resin composition according to any one of claims 1 to 5. A bonded body adhered with the adhesive according to claim 11. An optical component having the bonded body according to claim 12.