WO2013183532A1

WO2013183532A1 - Resin composition for coating materials

Info

Publication number: WO2013183532A1
Application number: PCT/JP2013/065007
Authority: WO
Inventors: 慶次後藤; 貴子星野; 公彦依田
Original assignee: 電気化学工業株式会社
Priority date: 2012-06-06
Filing date: 2013-05-30
Publication date: 2013-12-12
Also published as: TW201404787A; CN104350111A; JPWO2013183532A1; KR102135467B1; JP6105574B2; KR20150024319A; CN104350111B; TWI574978B

Abstract

Provided is a resin composition for coating materials, which has high refractive index and high transparency without requiring the use of a solvent. The present invention provides (1) a resin composition for coating materials, which is characterized by containing a specific dinaphthothiophene compound that has one or more polymerizable functional groups having an ethylenically unsaturated double bond (component (A)), a monofunctional (meth)acrylate that contains one or more aromatic rings (component (B)), and a radical photopolymerization initiator (component (C)), and which is also characterized in that the content ratio of the component (A) is within the range of 15-60 parts by mass and the content ratio of the component (B) is within the range of 40-85 parts by mass.

Description

Resin composition for coating material

The present invention relates to a resin composition for a coating material used for various sensor elements, display elements and the like, and further to a high refractive index resin composition used for a high refractive index layer of an antireflection film or an optical waveguide film.

Conventionally, on the surfaces of glass, films and sheets used for sensor elements such as CCD and CMOS, and display elements such as displays, a coating layer made of an inorganic substance or an organic substance is provided for the purpose of protecting the surface. Furthermore, in recent years, a covering layer in which high refractive index layers and low refractive index layers are alternately stacked is used for the purpose of imparting functions such as antireflection and optical waveguide to the surface protective layer. This high refractive index layer contains a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia and alumina, and radical polymerizable monomers such as bisphenol A type epoxy (meth) acrylate and urethane (meth) acrylate. However, the high-refractive-index organic film that is cured by irradiating energy rays such as ultraviolet rays after coating is used according to the purpose, but the former inorganic film is in close contact when the substrate is a film or sheet. In recent years, photocurable high-refractive-index organic films blended with radically polymerizable monomers have been widely used. It is like that.

As a resin composition having a high refractive index applicable to a high refractive index layer used for an antireflection film or an optical waveguide film, for example, Patent Documents 1 to 3 disclose a resin composition using sulfur-containing (meth) acrylate. Also known are photocurable resin compositions. Further, for example, Patent Document 4 discloses an active energy ray-curable composition using urethane (meth) acrylate having a diphenyl sulfone structure.

JP-A-11-5952 JP 2002-97224 A JP 2006-526037 Gazette JP 2011-157543 A JP 2011-178985 A JP 2012-136576 A

However, in the case of sulfur-containing (meth) acrylate and urethane (meth) acrylate having a diphenylsulfone structure, which are the main components described in the above-mentioned patent documents, 4,4′-dimercaptodiphenyl sulfide dimethacrylate is a bisphenol A type. Although it has a higher refractive index than a compound having an aromatic ring such as epoxy (meth) acrylate, these compounds generally absorb light with a wavelength of 450 nm or less, so they are colored yellow and the transparency tends to decrease. There was a problem that it was difficult to adhere to.

As a compound having a high refractive index and high transparency with respect to the above-described problems, Patent Document 5 discloses a compound and a polymer having a dinaphthothiophene skeleton. In Examples of Patent Document 5, a photocured film prepared by diluting a photopolymerizable composition using dinaphthothiophene having an ethylenically unsaturated double bond with a solvent such as ethyl acetate is disclosed. (Paragraph number [0143]). However, due to the influence of the residual solvent, it may cause a decrease in strength and outgassing, and good reliability cannot be obtained, or crystalline components tend to precipitate in the composition when stored for a long time. , The refractive index fluctuates and the coating cannot be performed.

The present invention has been made in view of such circumstances, and provides a resin composition for a coating material that has a high refractive index and high transparency and does not require the use of a solvent.

According to the present invention,
(1) As a component (A), a dinaphthothiophene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1):

(In the general formula (1), each X is independently a single bond, a divalent organic group or a divalent atom, each R ¹ is independently a hydrogen atom or a methyl group, and c + d is C is an integer of 0 to 4, and d is an integer of 0 to 4. provided that X is a divalent organic group, X is an oxygen atom; An alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond or an alkylene group containing these bonds in the main chain, an arylene group, an aralkylene group, a divalent group which may contain a hetero atom consisting of a sulfur atom or a nitrogen atom A substituted aromatic group, a divalent substituted heteroaromatic group, a divalent substituted silyl group, and when X is a divalent atom, X may be an oxygen atom, a sulfur atom, or another atom. And a tin atom that may have a bond with other atoms A phosphorus atom that may have a bond, wherein X may be bonded to any of the substitutable carbon atoms in the naphthalene ring to which they are bonded, wherein (R) a or (R) b is means a or b identical or different substituents, which may be attached to any of the substitutable carbon atoms in the naphthalene ring to which they are attached, and each R is independently an organic A group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, a is an integer of 0 to 5, and b is an integer of 0 to 5 (It is an integer.)
(B) As a component, a monofunctional (meth) acrylate containing one or more aromatic rings,
(C) As a component, radical photopolymerization initiator,
The content of the component (A) is in the range of 15 to 60 parts by mass and the content of the component (B) is in the range of 40 to 85 parts by mass with respect to the total amount of the composition. A resin composition for a coating material is provided.

The present inventors have intensively studied to obtain a composition suitable for the resin composition for a coating material. As a result, the dinaphthothiophene compound as shown in the general formula (1) does not use a solvent. When mixed with a polyfunctional epoxy acrylate and a radical photopolymerization initiator as described in [0143] of Patent Document 5, a precipitate that does not easily dissolve is generated after standing for a while, as a resin composition for a coating material. It was found that it was difficult to use (Comparative Example 2). Accordingly, further investigations have been made to solve such problems. When a monofunctional (meth) acrylate containing one or more aromatic rings is used in place of the polyfunctional epoxy acrylate, this is the case. It was found that no precipitates or separations were generated, or even if generated, they could be easily dissolved. Further, when a compound having an aromatic ring but not (meth) acrylate is used instead of a monofunctional (meth) acrylate containing an aromatic ring (Comparative Example 3), sufficient curing occurs even when light irradiation is performed. Therefore, it was found that it was difficult to use as a resin composition for a coating material. Furthermore, when a monofunctional (meth) acrylate having no aromatic ring was used (Comparative Example 4), a precipitate that was not easily dissolved was generated.
Further, when a dinaphthothiophene compound having no functional group is used instead of the dinaphthothiophene compound having a polymerizable functional group (Comparative Example 5), a precipitate that does not easily dissolve is generated. I have. Furthermore, when a dinaphthothiophene compound was not used (Comparative Example 1), the refractive index was low.
From the above, high refractive index and high transparency are achieved by the synergistic effect of the combination of a dinaphthothiophene compound having a polymerizable functional group, a monofunctional (meth) acrylate containing an aromatic ring, and a photo radical polymerization initiator. It has been found that a resin composition for a coating material that has a solvent and does not require the use of a solvent can be obtained.

Preferably, the component (B) is a monofunctional (meth) acrylate containing one aromatic ring.
Preferably, the component (B) includes one or more selected from benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Preferably, the polymerizable functional group is a (meth) acryloyl group or an allyl ether group.
Preferably, in the general formula (1), a = b = c = 0 and d = 1.
Preferably, the component (A) is 6- (meth) acryloylmethyldinaphthothiophene, 6- (meth) acryloylethyldinaphthothiophene, 2,12-diallyl ether dinaphthothiophene, and 3,11-diallyl ether diene. Including one or more selected from naphthothiophene.
Preferably, the content ratio of the component (C) is 0.2 to 10 parts by mass with respect to the total amount of the composition.

According to another aspect of the present invention, there is provided a covering material comprising the above-described resin composition for a covering material, and a base material (eg, glass, film or sheet) on which the covering material is formed. Provided.

According to still another aspect of the present invention, a layer having a refractive index lower than that of the above-mentioned resin composition for a coating material is formed after a layer made of the above-described resin composition for a coating material is formed on a substrate. Provided is a film formed by being formed (eg, an antireflection film or an optical waveguide film), a base material having such a film, and an element (eg, sensor element or display element) having such a base material Is done.

The resin composition of the present invention comprises a resin composition for a coating material containing a dinaphthothiophene compound having a polymerizable functional group, a monofunctional (meth) acrylate having an aromatic ring, and a radical polymerization initiator in a specific ratio. Therefore, it has characteristics such as high refractive index and transparency required for surface protection of sensor elements, display elements, antireflection films, optical waveguide films, and the like, and excellent adhesion. Moreover, since the resin composition for coating | covering material of this invention does not need to use a solvent, the strength fall by the influence of a residual solvent and the problem of outgas generation | occurrence | production can be avoided.

<Explanation of terms>
In this specification, a coating material is a coating on a substrate such as a glass substrate, a plastic film, or a plastic sheet for the purpose of imparting surface protection, designability, and functionality such as antireflection or optical waveguide. Means the material to be.

The components of the resin composition according to this embodiment will be described.

The energy beam curable resin composition according to the present embodiment has a difunctional dimer having one or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1) as the component (A). It has a naphthothiophene compound.

(In the general formula (1), each X is independently a single bond, a divalent organic group or a divalent atom, each R ¹ is independently a hydrogen atom or a methyl group, and c + d is C is an integer of 0 to 4, and d is an integer of 0 to 4. provided that X is a divalent organic group, X is an oxygen atom; An alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond, or an alkylene group containing these bonds in the main chain, an arylene group, an aralkylene group, a divalent group that may contain a hetero atom consisting of a sulfur atom or a nitrogen atom A substituted aromatic group, a divalent substituted heteroaromatic group, a divalent substituted silyl group, and when X is a divalent atom, X may be an oxygen atom, a sulfur atom, or another atom. And a tin atom that may have a bond with other atoms A phosphorus atom that may have a bond, wherein X may be bonded to any of the substitutable carbon atoms in the naphthalene ring to which they are bonded, wherein (R) a or (R) b is means a or b identical or different substituents, which may be attached to any of the substitutable carbon atoms in the naphthalene ring to which they are attached, and each R is independently an organic A group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, a is an integer of 0 to 5, and b is an integer of 0 to 5 (It is an integer.)

Examples of the polymerizable functional group include a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, a (meth) acrylonitrile group, etc., but transparency and adhesion to a substrate. In this respect, a (meth) acryloyl group or an allyl ether group is preferable, and a (meth) acryloyl group is particularly preferable.

Specific examples of the dinaphthothiophene compound include 6-vinyldinaphthothiophene, 6- (meth) acryloyloxymethyldinaphthothiophene, 6- (meth) acryloyloxyethyl dinaphthothiophene, 6-vinyl ether dinaphthothiophene, 6-allyldinaphthothiophene, 6-allyloxydinaphthothiophene, 2,12-divinyldinaphthothiophene, 3,11-divinyldinaphthothiophene, 5,9-divinyldinaphthothiophene, 2,12-di (meth) Acryloyloxymethyldinaphthothiophene, 3,11-di (meth) acryloyloxymethyldinaphthothiophene, 2,12-diallyloxymethyldinaphthothiophene, 3,11-diallyloxydinaphthothiophene, 2,12-divinyloxymethyl Genaf Examples thereof include thiophene and 3,11-divinyloxydinaphthothiophene. From the viewpoint of transparency, 6- (meth) acryloyloxymethyldinaphthothiophene, 6- (meth) acryloyloxyethyl dinaphthothiophene, 2,12 -Diallyloxydinaphthothiophene and 3,11-diallyloxydinaphthothiophene are preferred, and 6- (meth) acryloyloxymethyldinaphthothiophene is particularly preferred.

The content ratio of the component (A) is preferably 15 to 60 parts by mass with respect to the total amount of the resin composition. Particularly, the refractive index, transparency, adhesion to the substrate, and compatibility with the component (B). In this respect, 15 to 50 parts by mass is more preferable, 17 to 50 parts by mass is further preferable, and 20 to 40 parts by mass is most preferable. Here, the total amount of the resin composition is preferably 100 parts by mass in total of the component (A) and the component (B).

The dinaphthothiophene-based compound can be produced by a production method exemplified in Japanese Patent Application Laid-Open No. 2011-178985 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2012-136576 (Patent Document 6). A product manufactured by any manufacturing method is not limited.

<(B) component: monofunctional (meth) acrylate>
The resin composition of the present invention contains a monofunctional (meth) acrylate having one or more aromatic rings as the component (B). The number of aromatic rings is, for example, 1, 2, 3, and preferably one.

Specific examples of the monofunctional (meth) acrylate include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, and phenoxyhexaethylene glycol (meth) acrylate. , Nonylphenyl (meth) acrylate, ethylene oxide modified nonylphenyl (meth) acrylate, phthalic acid modified (meth) acrylate, naphthyl (meth) acrylate, bisphenylfluorene (meth) acrylate, 2- (o-phenylphenoxy) ethyl ( (Meth) acrylate and the like can be exemplified, but from the viewpoint of compatibility with the component (A), refractive index, and transparency, benzyl (meth) acrylate and / or phenoxyethyl (meth) ) Acrylate is particularly preferred.

The content ratio of the component (B) is preferably 40 to 85 parts by mass with respect to the total amount of the resin composition, particularly the refractive index, transparency, adhesion to the substrate, and compatibility with the component (A). In this respect, 50 to 85 parts by mass is more preferable, 50 to 83 parts by mass is further preferable, and 60 to 80 parts by mass is most preferable.

The resin composition of the present invention may contain a monofunctional (meth) acrylate compound having no aromatic ring or a polyfunctional (meth) acrylate as long as the effects of the invention are not impaired.

<(C) component: radical photopolymerization initiator>
The resin composition of the present embodiment contains (C) a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.

Examples of the photo radical polymerization initiator include benzyl 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, and 2,2-diethoxy Alkyl acetophenone derivatives such as acetophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -Phenyl) -2-hydroxy-2-methyl-1-propan-1-one, α-hydroxyacetophenone derivatives such as 2-hydroxy-2-methyl-1-phenylpropan-1-one Bisdiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Α-Aminoalkylacetophenone derivatives such as butanone-1, isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester Esters, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphine Methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, bivaloyl- (4-methylphenyl) -phosphinic acid methyl ester, pivaloyl-phenylphosphinic acid vinyl ester, (meth) acryloyl-phenylphosphinic acid methyl ester Ester, isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-1-cyclohexanoyl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide , O-Toluyl-diphenylphosphine oxide, p-tert-butylbenzoyl-diphenylphosphine oxide, (meth) acryloyl diphe Nylphosphine oxide, benzoyl-diphenylphosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, 2,6-dimethylbenzoyl- Diphenylphosphine oxide, 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphosphine oxide, 2,4,6-trimethyl Benzoyl-phenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoy -Diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-triphosphinic acid methyl ester, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-phenylphosphinic acid ester, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,4,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,6-dimethylbenzoyldiphenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-young 2,6-dimethoxybenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine Acylphosphine oxide derivatives such as oxide, 1,2-octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2- And oxime ester compounds such as methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). Among these, one or more of alkyl acetophenone derivatives, α-hydroxyacetophenones, and phosphine oxides are preferable in terms of excellent reactivity and transparency. These can be used alone or in combination of two or more.

The content of component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on the total amount of the resin composition. If it is in the range of 0.1 to 10 parts by mass, the curability will not be deteriorated and the transparency will not be lowered.

<Other additives>
As long as the purpose of the present embodiment is not impaired, an antioxidant, a silane coupling agent, various elastomers such as an acrylic rubber and a urethane rubber, a photosensitizer, a light stabilizer, a solvent, an extender, a filler, a reinforcing material, You may contain additives, such as a plasticizer, a thickener, a dye, a pigment, a flame retardant, and surfactant.

The method for producing the resin composition according to this embodiment is not particularly limited as long as the above materials can be sufficiently mixed. The mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.

After the above mixing, the resin composition can be cured by irradiation with 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 is a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultra-high pressure. Examples thereof include a mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and a light emitting diode (hereinafter referred to as LED). These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective radical photopolymerization initiators.

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

The light source may perform direct irradiation, focused irradiation with a reflecting mirror or the like, or focused irradiation with a fiber or the like. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.

Since the resin composition having the above-mentioned structure is quickly cured by irradiation with energy rays, a cured product excellent in optical properties such as high transparency and high refractive index can be provided.

In addition, the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and has excellent adhesion to substrates such as glass, plastic film, and plastic sheet. Can be offered as.

Furthermore, since the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, it can be used as a high refractive index layer of an antireflection film or an optical waveguide film. An optical waveguide film can be provided.

The antireflection film and optical waveguide film are coated with a layer made of the resin composition of the present invention (hereinafter referred to as a high refractive index layer) on various substrates such as glass, plastic film, plastic sheet, etc., and irradiated with energy rays. Then, a layer having a lower refractive index than the high refractive index layer (hereinafter referred to as a low refractive index layer) is formed on the high refractive index layer.

Base materials 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, and metals such as silicone, aluminum, stainless steel, iron, copper, and silver. From resins such as base materials, acrylic resins, styrene resins, carbonate resins, olefin resins, polyester resins, polyimide resins, polyamide resins, epoxy resins, silicone resins, fluorine resins, and cellulose resins A film base material, a sheet base material, and the like can be used.

Examples of the low refractive index layer include inorganic films such as alkali metal fluorides such as magnesium fluoride and potassium fluoride, silica, and the like, and organic films such as fluoropolymers such as polyperfluoroethylene and perfluorocycloolefin. Polyether resins such as polyethylene glycol, silicone resins, acrylic resins, epoxy resins, urethane resins and their fluorine-modified resins can be used.

The resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and therefore has a high liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smartphone, a mobile phone, a digital camera, a digital movie display element, It can be used as a coating material used for various sensor parts such as CCD, CMOS, and biochip, semiconductor elements such as flash memory, DRAM, and semiconductor laser, and also as a high refractive index layer of an antireflection film or an optical waveguide film.

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

In the examples, the following compounds were used.

(A) Dinaphthothiophene compound The dinaphthothiophene compound used was prepared by the synthesis method described in JP2011-178985 (Patent Document 5) ([Example] [0106] to [0121]). .
(A-1) 6-Methacryloyloxymethyldinaphthothiophene (abbreviation: DNTMA)
(A-2) 6-vinyldinaphthothiophene (abbreviation: VDNT)
(A-3) 6-methacryloyloxyethyldinaphthothiophene (abbreviation: EDNTMA)
(A-4) 2,12-diallyloxydinaphthothiophene (abbreviation: DAODNT)
(A-5) 3,11-diallyloxydinaphthothiophene (abbreviation: i-DAODNT)
(A-6) Dinaphthothiophene (abbreviation: DNT)

(B) Monofunctional (meth) acrylate having an aromatic ring (B-1) benzyl methacrylate (“Light Ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.)
(B-2) Benzyl acrylate (Osaka Organic Chemical Co., Ltd. “Biscoat # 160”)
(B-3) Phenoxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester PO”)
(B-4) Phenoxyethyl acrylate (“Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd.)
(B-5) 2- (o-phenylphenoxy) ethyl acrylate (“NK Ester A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd.)

(C) Photoradical polymerization initiator (C-1) Benzyldimethyl ketal (“IRGACURE 651” manufactured by BASF)
(C-2) 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure 184” manufactured by BASF)
(C-3) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF)

The following were used as other compounds.
(D-1) Bisphenol A type epoxy acrylate (“Epoxy ester 3002M” manufactured by Kyoeisha Chemical Co., Ltd.)
(D-2) Styrene (“Styrene” manufactured by Wako Pure Chemical Industries, Ltd.)
(D-3) Methyl methacrylate (Mitsubishi Gas Chemical "MMA")
(D-4) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (“BPFEA” manufactured by Osaka Gas Chemical Company)

(Examples 1 to 18, Comparative Examples 1 to 6)
The raw materials of the types shown in Tables 1 to 3 were mixed in the composition ratios (units are parts by mass) shown in Tables 1 to 3, to prepare resin compositions for coating materials, and the evaluation described below was performed. No solvent was used. Various evaluation results are shown in Tables 1 to 3. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.

(Liquid stability evaluation)
Prepare a sealed sample by placing 10 ml of the resin composition in a 30 ml vial, leave the sample in an atmosphere at a temperature of 23 ° C. for 24 hours, visually check the liquid state after 24 hours, and use the following criteria: evaluated.
◯: No change from before standing Δ: Precipitates and isolates were seen but redissolved by heating at 50 ° C. x: Precipitates and isolates were seen and did not dissolve again even at 50 ° C. The state of the liquid after mixing was visually confirmed, and subsequent evaluation was not carried out for the sample in which precipitates and separated matters were observed.

(Evaluation of refractive index)
(1) Liquid Refractive Index The liquid refractive index was evaluated by measuring the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm using a multi-wavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
(2) Refractive index of cured product The resin composition was poured into a silicone rubber mold having a volume of 15 mm × 15 mm × 1.0 mm, and a film having a thickness of 365 nm was measured using an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA). A cured product test piece cured under conditions of an irradiation intensity of a wavelength of 30 mW / cm ² and an integrated light amount of 30,000 mJ / cm ² was prepared, and a refractive index was evaluated. The refractive index was evaluated by measuring the refractive index at a wavelength of 633 nm using a spectroscopic prism coupler refractive index measuring device ("MODEL 2010 PRISM COUPLER" manufactured by Metricon).

(Spectral transmittance measurement)
The resin composition was applied on a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) with a film thickness of 30 μm, and then an ultra-high pressure mercury lamp mounting device (“UL-” manufactured by HOYA). 750 "), a test piece cured under the conditions of an irradiation intensity of a wavelength of 365 nm of 50 mW / cm ² and an integrated light quantity of 30,000 mJ / cm ² was prepared, and an ultraviolet-visible spectrophotometer (Shimadzu Corporation" UV " -2550 "), and the transmittance was measured at 450 nm using a heat resistant glass as a reference.

[Adhesion evaluation (cross cut test)]
On a polyester film of 125 μm thickness (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.), the resin composition was irradiated with an ultra-high pressure mercury lamp (“UL-750” manufactured by HOYA) with an irradiation intensity of 50 nm at a wavelength of 365 nm. ^2. A test piece was prepared in which a cured film of a resin composition having a shape of 20 mm × 20 mm × 80 μm was formed by curing under the condition of an integrated light quantity of 30,000 mJ / cm ² and a nitrogen atmosphere.
For each test piece obtained in this manner, a cut line was placed in the cured film so as to be 2 mm long × 2 mm wide × 25 squares in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then cellophane. A tape (model CT-405AP manufactured by Nichiban Co., Ltd .: width 24 mm, adhesive strength 23 N / 10 mm) was applied and 180 ° peeling was performed. The number of cells remaining after 180 ° peeling was counted and evaluated according to the following criteria. Other conditions that were not specified were in accordance with JIS K 5600-5-6.
○: All 25 sheets remained Δ: 15 or more and 24 or less remained x: Less than 14 sheets

<Discussion>
In Examples 1 to 18, excellent results were obtained in terms of liquid stability, refractive index, spectral transmittance, and adhesion. However, in Example 1, since the blending ratio of the dinaphthothiophene compound was small, the refractive index was slightly low. In Example 6, since the compounding ratio of the dinaphthothiophene compound was large, the liquid stability and adhesion were slightly deteriorated. In Example 10 using a dinaphthothiophene compound having a vinyl group, Examples 1 to 9 and Examples 11 to 14 using a dinaphthothiophene compound having a (meth) acryloyl group or an allyl ether group were used. In comparison, liquid stability, spectral transmittance and adhesion were not preferred. This result shows the advantage of using a dinaphthothiophene compound having a (meth) acryloyl group or an allyl ether group. Further, comparing Example 3 with Examples 11 to 13, it was found that when DNTMA was used as in Example 3, the refractive index and spectral transmittance were particularly high. Furthermore, as in Example 14, when an acrylate having two aromatic rings was used as the component (B), the liquid stability, spectral transmittance, and adhesion were deteriorated.

In Comparative Example 1, since the dinaphthothiophene compound was not used, the refractive index was not sufficient. In Comparative Example 2, since polyfunctional acrylate (bisphenol A type epoxy acrylate) was used, the liquid stability was very poor, and a test piece for evaluation of refractive index and spectral transmittance could not be prepared. In Comparative Example 3, since a compound (styrene) having an aromatic ring but not (meth) acrylate was used instead of the component (B), curing did not occur sufficiently even when light irradiation was performed. In Comparative Example 4, since monofunctional (meth) acrylate (methyl methacrylate) having no aromatic ring was used instead of component (B), the liquid stability was poor and precipitates that did not dissolve easily were generated. It was. In Comparative Example 5, since a dinaphthothiophene compound (dinaphthothiophene) having no functional group was used, the liquid stability was poor and precipitates that were not easily dissolved were generated. In Comparative Example 6, since there was too little (B) component, the liquid stability was bad and the precipitate which does not melt | dissolve easily occurred.

Since the resin composition of the present invention is excellent in optical properties such as high transparency and high refractive index, a high liquid crystal panel, organic electroluminescence panel, touch panel, projector, smartphone, mobile phone, digital camera, digital movie display element, Suitable for use as sensor elements for various sensor components such as CCD, CMOS, biochip, coating materials used for semiconductor elements such as flash memory, DRAM, and semiconductor laser, and as a high refractive index layer for antireflection films and optical waveguide films. Can be very useful in industry.

Claims

As the component (A), a dinaphthothiophene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1):

(In the general formula (1), each X is independently a single bond, a divalent organic group or a divalent atom, each R 1 is independently a hydrogen atom or a methyl group, and c + d is C is an integer of 0 to 4, and d is an integer of 0 to 4. provided that X is a divalent organic group, X is an oxygen atom; An alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond, or an alkylene group containing these bonds in the main chain, an arylene group, an aralkylene group, a divalent group that may contain a hetero atom consisting of a sulfur atom or a nitrogen atom A substituted aromatic group, a divalent substituted heteroaromatic group, a divalent substituted silyl group, and when X is a divalent atom, X may be an oxygen atom, a sulfur atom, or another atom. And a tin atom that may have a bond with other atoms A phosphorus atom that may have a bond, wherein X may be bonded to any of the substitutable carbon atoms in the naphthalene ring to which they are bonded, wherein (R) a or (R) b is means a or b identical or different substituents, which may be attached to any of the substitutable carbon atoms in the naphthalene ring to which they are attached, and each R is independently an organic A group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, a is an integer of 0 to 5, and b is an integer of 0 to 5 (It is an integer.)
(B) As a component, a monofunctional (meth) acrylate containing one or more aromatic rings,
(C) As a component, radical photopolymerization initiator,
The content of the component (A) is in the range of 15 to 60 parts by mass and the content of the component (B) is in the range of 40 to 85 parts by mass with respect to the total amount of the composition. A resin composition for a coating material.
The resin composition for a coating material according to claim 1, wherein the component (B) is a monofunctional (meth) acrylate containing one aromatic ring.
The resin composition for a coating material according to claim 1 or 2, wherein the component (B) includes one or more selected from benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
The resin composition for a covering material according to any one of claims 1 to 3, wherein the polymerizable functional group is a (meth) acryloyl group or an allyl ether group.
The resin composition for a coating material according to any one of claims 1 to 3, wherein, in the general formula (1), a = b = c = 0 and d = 1.
The component (A) is 6- (meth) acryloyloxymethyldinaphthothiophene, 6- (meth) acryloyloxyethyl dinaphthothiophene, 2,12-diallyloxydinaphthothiophene, and 3,11-diallyloxydinaphtho The resin composition for a coating material according to any one of claims 1 to 5, comprising one or more selected from thiophene.
The resin composition for a coating material according to any one of claims 1 to 6, wherein a content ratio of the component (C) is 0.2 to 10 parts by mass with respect to a total amount of the composition.
A coating material comprising the resin composition for a coating material according to any one of claims 1 to 7.
A base material on which the coating material according to claim 8 is formed.
A layer having a refractive index lower than that of the resin composition for a coating material is formed after forming the layer made of the resin composition for a coating material according to any one of claims 1 to 7 on the substrate. A film characterized by.
A substrate having the film according to claim 10.
An element having the base material according to claim 11.