JPWO2015029996A1 - Resin composition for coating material - Google Patents

Abstract

Provided is a resin composition for a coating material which has a high refractive index and high transparency and does not require the use of a solvent. According to the present invention, (1) a specific dinaphthothiophene polyene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond as the component (A), and a polythiol compound as the component (B) A radical polymerization initiator as component (C), and a polyene compound other than dinaphthothiophene and having a smaller number of carbon atoms than component (A) as component (D), and component (A) The content ratio is 5 to 50 parts by mass with respect to the total amount of the composition, the content ratio of the component (B) is 10 to 60 parts by mass with respect to the total amount of the composition, and (D The content ratio of the component is in the range of 5 to 85 parts by mass with respect to the total amount of the composition.

Description

  The present invention relates to a resin composition for a coating material used for various sensor elements, display elements and the like, and further relates 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, in Patent Documents 1 to 3, a resin composition using a sulfur-containing (meth) acrylate is used. 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 Japanese Patent Laid-Open No. 2002-97224 JP 2006-526037 A JP 2011-157543 A JP 2011-178985 A JP 2012-136576 A

Polymer Science Society Proceedings Vol. 61, p4695-4696 (Preliminary Proceedings at the 61st Polymer Symposium (Sponsored by the Society of Polymer Science) held on September 20, 2012)

  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 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.

  This invention is made | formed in view of such a situation, and provides the resin composition for coating | covering materials which 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 polyene compound having two or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the general formula (1) described later,
(B) As a component, a polythiol compound,
(C) As a component, radical photopolymerization initiator,
As the component (D), a polyene compound that is other than dinaphthothiophene and has fewer carbon atoms than the component (A),
The content ratio of the component (A) is in the range of 5 to 50 parts by mass with respect to the total amount of the composition, and the content ratio of the component (B) is 10 to 60 masses with respect to the total amount of the composition. A resin composition for a coating material is provided, wherein the content ratio of the component (D) is in the range of 5 to 85 parts by mass with respect to the total amount of the composition.

Preferably, a polymerization inhibitor is further contained as component (E).
Preferably, the polymerizable functional group of the component (A) is one selected from the group consisting of a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, or a (meth) acrylonitrile group. More than a seed.
Preferably, the polymerizable functional group is an allyl ether group.
Preferably, in the general formula (1), a = b = 0 and c = d = 1.
Preferably, the component (A) includes 2,12-diallyl ether dinaphthothiophene.
Preferably, the component (D) has 6 to 23 carbon atoms.
Preferably, the component (D) is at least one member selected from the group consisting of (meth) acrylates, allyl compounds, and allyl ether compounds.

  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 for a coating material of the present invention comprises a resin composition for a coating material containing a dinaphthothiophene-based polyene compound having two or more polymerizable functional groups, a polythiol compound, 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 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 and optical waveguide. Means the material to be. In this specification, the “total amount of the resin composition” refers to a total of 100 parts by mass of the component (A), the component (B), and the component (D).

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

<(A) component: dinaphthothiophene polyene compound>
The energy ray-curable resin composition according to the present embodiment has, as component (A), dinaphtho having two or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1). It has a thiophene-based polyene compound.
(In the general formula (1), each Y is independently a polymerizable functional group represented by the general formula (2), and c is 1 to 2 on the condition that c + d is an integer of 2 to 4. 3 is an integer of 3 and d is an integer of 1 to 3. (R) a or (R) b means a or b identical or different substituents, respectively. Each R may be independently bonded to an organic group, hydroxyl group, amino group, nitro group, thiol group, sulfo group, halogen atom, or substituted atom. And a is an integer of 0 to 5, and b is an integer of 0 to 5.
In the general formula (2), 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 X is 2 In the case of a valent organic group, X represents an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond or a bond thereof that may contain a hetero atom consisting of an oxygen atom, a sulfur atom or a nitrogen atom. An alkylene group, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, and a divalent substituted silyl group included in the main chain. When X is a divalent atom, X is an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus atom that may have a bond with another atom. is there. X may be bonded to any substitutable carbon atom in the naphthalene ring to which they are bonded. )

  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, and the like in terms of transparency and reactivity ( A (meth) acryloyl group or an allyl ether group is preferred, and an allyl ether group is particularly preferred.

  Specific examples of the dinaphthothiophene compound include 2,12-divinyldinaphthothiophene, 3,11-divinyldinaphthothiophene, 5,9-divinyldinaphthothiophene, 2,12-diacryloylmethyldinaphthothiophene, 3,11-Diacryloylmethyldinaphthothiophene, 2,12-dimethacryloylmethyldinaphthothiophene, 3,11-dimethacryloylmethyldinaphthothiophene, 2,12-diallyl ether methyldinaphthothiophene, 3,11-diallyl ether Dinaphthothiophene, 2,12-divinyl ether methyldinaphthothiophene, 3,11-divinyl ether dinaphthothiophene, 2,12-dimethacryloyloxyethoxydinaphthothiophene, 2,12-dimethacryloyloxypropoxydinaphth Examples include thiophene, 2,12-diacryloyloxyethoxydinaphthothiophene, 2,12-diacryloyloxypropioxydinaphthothiophene, etc., but in terms of compatibility with component (B), 2,12- 2,12-Diacryloylmethyldinaphthothiophene, 2,12-dimethacryloylmethyldinaphthothiophene, 2,12-diallyl ether dinaphthothiophene, 2,12-dimethacryloyloxyethoxydinaphthothiophene, 2 , 12-Dimethacryloyloxypropioxydinaphththiophene, 2,12-diacryloyloxyethoxydinaphthothiophene, 2,12-diacryloyloxypropioxydinaphthothiophene are preferable, and the reactivity with the component (B) 2,12-diallyl ether dinaphthothiophene Preferred.

  The content ratio of the component (A) is preferably 5 to 50 parts by mass with respect to the total amount of the resin composition, and particularly 15 to 45 parts by mass in terms of compatibility between the high refractive index and the component (B). Is more preferable. Specifically, the content ratio of the component (A) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and between any two of the numerical values exemplified here. It may be within the range.

  Although the said dinaphtho thiophene type polyene compound can be manufactured with the manufacturing method illustrated by patent documents 5-6 or nonpatent literature 1, what was manufactured by what kind of manufacturing method is not restricted to this method.

<(B) component: polythiol compound>
The resin composition of the present invention contains a polythiol compound as the component (B).

  The polythiol compound used in the present invention is a substance having an average molecular weight of 50 to 15000 having two or more thiol groups per molecule.

  Specific examples of the polythiol compound used in the present invention include mercapto group-substituted alkyl compounds such as dimercaptobutane and trimercaptohexane, mercapto group-substituted allyl compounds such as dimercaptobenzene, trimethylolpropane-tris- (β -Thiopropionate), tris-2-hydroxyethyl-isocyanurate tris-β-mercaptopropionate, pentaerythritol tetrakis (β-thiopropionate) and other polyhydric alcohols such as thioglycolic acid and thiopropionic acid Esters, and 1,8-dimercapto-3,6-dioxaoctane, 1,11-dimercapto 3,6,9-trioxadodecane, diethylene glycol bisthioglycolate, triethylene glycol bisthioglycolate, tetraethy Glycol bisthioglycolate, pentaethylene glycol bisthioglycolate, hexaethylene glycol bisthioglycolate, octaethylene glycol bisthioglycolate, dodecane ethylene glycol bisthioglycolate, diethylene glycol bis (3-mercaptopropionate), Triethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), pentaethylene glycol bis (3-mercaptopropionate), hexaethylene glycol bis (3-mercaptopropionate) ), Octaethylene glycol bis (3-mercaptopropionate), dodecane ethylene glycol bis (3-mercaptopropionate), diethylene glycol Bis (3-mercaptobutyrate), triethylene glycol bis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptobutyrate), pentaethylene glycol bis (3-mercaptobutyrate), hexaethylene glycol bis ( 3-mercaptobutyrate), octaethylene glycol bis (3-mercaptobutyrate), dodecane ethylene glycol bis (3-mercaptobutyrate), polyethylene glycol bisthioglycolate, polyethylene glycol bis (3-mercaptopropionate), Polyethylene glycol bis (3-mercaptobutyrate), polypropylene glycol bisthioglycolate, polypropylene glycol bis (3-mercaptopropionate), polypropylene Ethylene glycol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane-tris- (3-mercaptopropinate) ethylene oxide adduct, tris-[(3 -Mercaptopropionyloxy) -ethyl] -isocyanurate ethylene oxide adduct, pentaerythritol tetrakis (3-mercaptopropionate) ethylene oxide adduct, pentaerythritol tetrakis (3-mercaptobutyrate) ethylene oxide adduct, Ethylene oxide adduct of trimethylolethanetris (3-mercaptobutyrate), 1,8-dimercapto-3,6-dioxaoctane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1, 3,5-G Reaction of hydrogen sulfide with alkylene oxide adducts of polyhydric alcohols such as ethylene oxide adducts of azine-2,4,6 (1H, 3H, 5H) -trione, dipentaerythritol hexakis (3-mercaptopropionate) Products, others, 1,8-dimercapto-3,6-disulfide octane, triazine thiol and the like can be mentioned. Among these, from the viewpoint of high refractive index and compatibility with the component (A), a reaction product of an alkylene oxide adduct and hydrogen sulfide is preferable, and 1,8-dimercapto-3,6-dioxaoctane is particularly preferable.

  The content ratio of the component (B) is preferably 10 to 60 parts by mass with respect to the total amount of the resin composition, particularly 20 to 50 parts by mass in terms of high refractive index and compatibility with the component (A). Is more preferable. Specifically, the content ratio of the component (B) is, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 parts by mass, and any of the numerical values exemplified here is 2 It may be within a range between the two.

<(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. Alkylacetophenone derivatives such as acetophenone and 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, Sudiethylaminobenzophenone, 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 Ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphinic acid Tilester, p-3 tertiary butylbenzoyl-phenylphosphinic acid isopropyl ester, bivaloyl- (4-methylphenyl) -phosphinic acid methyl ester, pivaloyl-phenylphosphinic acid vinyl ester, (meth) acryloyl-phenylphosphinic acid methyl 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-3 tertiary butylbenzoyl-diphenylphosphine oxide, (meth) acryloyldipheny Ruphosphine oxide, benzoyl-diphenylphosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, 2,6-dimethylbenzoyl-diphenyl Phosphine 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-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-dimethylbenzoyldiphenylphosphine Fin oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl- or , 6-Dimethoxybenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide Acylphosphine oxide derivatives such as 1,2-octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methyl) And oxime ester compounds such as benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). In these, 1 or more types which consist of an alkyl acetophenone derivative, (alpha) -hydroxy acetophenone, and phosphine oxide are preferable at the point which is excellent in reactivity and transparency, and an acyl phosphine oxide derivative is more preferable. Among the acylphosphine oxide derivatives, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable. These can be used alone or in combination of two or more.

  (C) It is preferable to make the content rate of a component contain in the ratio of 0.1-10 mass parts with respect to the total amount of a resin composition, and 0.5-5 mass parts is especially more preferable. If it exists in the range of 0.1-10 mass parts, sclerosis | hardenability will not worsen and transparency will not fall. Specifically, the content ratio of the component (C) is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, and is exemplified here. It may be within a range between any two of the numerical values.

<(D) component: polyene compound other than dinaphthothiophene type>
The resin composition of the present invention contains a polyene compound other than dinaphthothiophene as component (D).

  Specific examples of polyene compounds other than dinaphthothiophene as the component (D) are not limited as long as they are alkenes having two or more carbon-carbon unsaturated bonds per molecule, but include divinylbenzene, divinyltoluene, and the like. Vinyl compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri ( (Meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, Diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, allyl compounds such as tetraallyloxyethane, allyl ethers such as polyoxypropylene diallyl ether compounds, and the like. Of the vinyl compounds, divinylbenzene is preferred. Among the (meth) acrylates, isocyanuric acid ethylene oxide-modified tri (meth) acrylate is preferable. Among allyl compounds, triallyl isocyanurate is preferable. Among these, a high refractive index is obtained, and the compatibility with (A) component and (B) component and the reactivity are excellent, and among the groups consisting of (meth) acrylates, allyl compounds, and allyl ether compounds. 1 or more types of these are preferable, 1 or more types in the group which consists of an allyl compound and an allyl ether compound are more preferable, and an allyl compound is the most preferable.

The number of carbon atoms of the component (D) is less than that of the component (A) from the viewpoint of compatibility with the components (A) and (B), and is, for example, 6 to 23, preferably 6 to 18. Specifically, the carbon number of the component (D) is, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23. It may be within the range between any two of the numerical values exemplified here. Even if the number of carbon atoms of the component (D) exceeds 23, the component (D) can be used if the number of carbon atoms of the component (D) is less than the number of carbon atoms of the component (A) used in this embodiment.
Although the molecular weight of (D) component is not specifically limited, For example, it is 100-700, for example, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, and may be within a range between any two of the numerical values exemplified here.

  The content ratio of the component (D) is preferably 5 to 85 parts by mass with respect to the total amount of the resin composition, and particularly has a high refractive index, transparency, and compatibility with the components (A) and (B). The point is more preferably 15 to 65 parts by mass. Specifically, the content ratio of the component (D) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 parts by mass. It may be within the range between any two of the numerical values exemplified here.

  Furthermore, the resin composition of the present invention includes a monofunctional (meth) acrylate compound, a monofunctional vinyl compound, a monofunctional vinyl ether compound, a monofunctional allyl ether compound, a monofunctional compound, as long as the effects of the invention are not impaired. A thiol compound may be contained.

<(E) component: Polymerization inhibitor>
The resin composition of the present invention may contain (E) a polymerization inhibitor for the purpose of imparting storage stability as long as the effects of the invention are not impaired. (E) As a polymerization inhibitor, 1 or more types in the group which consists of a quinone type compound and a nitrosamine type compound are preferable, and a nitrosamine type compound is more preferable. As quinone compounds, β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di- Examples include tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, and the like. Examples of the nitrosamine compound include N-nitrosophenylhydroxylamine ammonium salt (cuperon), N-nitrosophenylhydroxylamine aluminum salt, and the like. Among the quinone compounds, one or more members selected from the group consisting of hydroquinone and hydroquinone monomethyl ether are preferable. Among the nitrosamine compounds, one or more members selected from the group consisting of cuperone and N-nitrosophenylhydroxylamine aluminum salt are preferable, and N-nitrosophenylhydroxylamine aluminum salt is most preferable.

(E) 0.00001-1.0 mass part is preferable with respect to the total amount of a resin composition, as for content of a polymerization inhibitor, 0.0005-0.1 mass part is more preferable, 0.001-0. Most preferred is 01 parts by weight. (E) Specifically, the content of the polymerization inhibitor is, for example, 0.00001, 0.0001, 0.0005, 0.001, 0.002, 0.003, 0.004, 0.005, 0. .01, 0.1, and 1 part by mass, and may be within a range between any two of the numerical values exemplified here.

<Other additives>
As long as the purpose of the present embodiment is not impaired, various elastomers such as antioxidants, silane coupling agents, acrylic rubbers, urethane rubbers, diene rubbers, photosensitizers, light stabilizers, solvents, extenders, fillers Further, additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.

  About the manufacturing method of the resin composition which concerns on this embodiment, there will be no restriction | limiting in particular if said material can fully be 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 performing 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 and adhering the resin composition is not particularly limited, but 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, Examples include ultra-high pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, and light emitting diodes (hereinafter referred to as LEDs). These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective radical photopolymerization initiators.

  Each of the light sources has a different emission wavelength and energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the radical photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.

  The light source may perform direct irradiation, condensing irradiation using a reflecting mirror, or condensing irradiation using 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-described structure is quickly cured by irradiation with energy rays, a cured product having excellent optical characteristics 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-based polyene compound As the dinaphthothiophene-based polyene compound, one produced by the synthesis method described in Non-Patent Document 1 was used.
(A-1) 2,12-diallyl ether dinaphthothiophene (abbreviation: DAODNT)

(B) Polythiol compound (B-1) 1,8-dimercapto-3,6-dioxaoctane ("DMDO" manufactured by Maruzen Petrochemical Co., Ltd., abbreviation: DMDO)
(B-2) Trimethylolpropane-tris- (β-thiopropinate) (“TMMP-20P”, abbreviation: TMMP, manufactured by SC Organic Chemical Co., Ltd.)
(B-3) Pentaerythritol tetrakis (3-mercaptopropionate) ("PEMP" manufactured by SC Organic Chemicals, abbreviation: PEMP)
(B-4) Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (“TEMPIC”, abbreviated as TEMPIC, manufactured by SC Organic Chemical Co., Ltd.)

(C) Photoradical polymerization initiator (C-1) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF, abbreviation: BAPO)

(D) Polyene compounds other than dinaphthothiophene series (D-1) triallyl isocyanurate (carbon number 12, “TAIC” manufactured by Nippon Kasei Co., Ltd., abbreviation: TAIC)
(D-2) Isocyanuric acid ethylene oxide-modified triacrylate (18 carbon atoms, “Aronix M-315” manufactured by Toa Gosei Co., Ltd., abbreviation: TAEOC)
(D-3) Divinylbenzene (8 carbon atoms, “Divinylbenzene” manufactured by Tokyo Chemical Industry Co., Ltd., abbreviation: DVB)
(D-4) Dipentaerythritol hexaacrylate (carbon number 28, “Light acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd., abbreviation: DPHA, (D-4) is used as a comparative example because it has a large number of carbon atoms)

(E) Polymerization inhibitor (E-1) N-nitrosophenylhydroxylamine aluminum salt (“Q-1301”, abbreviation: NPHAA, manufactured by Wako Pure Chemical Industries, Ltd.)

(Examples 1-13, Comparative Examples 1-4)
The raw materials of the type shown in Table 1 were mixed at the composition ratio (unit is parts by mass) shown in Table 1, to prepare a resin composition for a coating material, and the evaluation described below was performed. No solvent was used. Various evaluation results are shown in Table 1. 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 multiwavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
(2) Refractive index of cured product The adhesive composition was poured into a silicone rubber mold having a volume of 15 mm × 15 mm × 1.0 mm, and 365 nm with an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA). A cured product test piece cured under the conditions of an irradiation intensity of 30 mW / cm ² and an integrated light quantity of 30,000 mJ / cm ² was prepared, and the 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)
After applying the adhesive composition on 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, an ultra-high pressure mercury lamp mounting device (“UL” manufactured by HOYA -750 "), a test piece cured under conditions of irradiation intensity of a wavelength of 365 nm of 50 mW / cm ² and integrated light quantity of 30,000 mJ / cm ² was prepared, and an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation) UV-2550 "), 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 a wavelength of 365 nm of 50 mW / cm. ^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. The tape (Nichiban Co., Ltd. model CT-405AP: width 24mm, adhesive strength 23N / 10mm) was affixed and 180 degree peeling was implemented. The number of cells remaining after 180 ° peeling was counted and evaluated according to the following criteria. Other conditions not specified in particular 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 13, excellent results were obtained in terms of liquid stability, refractive index, spectral transmittance, and adhesion. However, in Examples 1-2, since there were few compounding quantities of (D) component, liquid stability was a little inferior. In Example 8, since there were few dinaphthothiophene-type polyene compounds, in Example 13, since the vinyl compound was used as (D) component, the adhesiveness of the cured film was a little inferior.

  In Comparative Example 1, since the dinaphthothiophene polyene compound was not used, the refractive index and the adhesion of the cured film were not sufficient. In Comparative Example 2, since the blending amount of the dinaphthothiophene polyene compound was too large, in Comparative Example 3, since the polyene compound other than the dinaphthothiophene compound was not blended, the liquid stability was poor and it was not easily redissolved. Since precipitates were generated, a test piece for evaluation could not be prepared. In Comparative Example 4, a polyene compound other than the dinaphthothiophene compound was blended. However, because the polyene compound has too many carbon atoms, a precipitate that does not easily re-dissolve due to poor liquid stability was generated. The test piece could not be made.

  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 (15)

As the component (A), a dinaphthothiophene-based polyene compound having two or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1):
(In the general formula (1), each Y is independently a polymerizable functional group represented by the general formula (2), and c is 1 to 2 on the condition that c + d is an integer of 2 to 4. 3 is an integer of 3 and d is an integer of 1 to 3. (R) a or (R) b means a or b identical or different substituents, respectively. Each R may be independently bonded to an organic group, hydroxyl group, amino group, nitro group, thiol group, sulfo group, halogen atom, or substituted atom. And a is an integer of 0 to 5, and b is an integer of 0 to 5.
In the general formula (2), 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 X is 2 In the case of a valent organic group, X represents an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond or a bond thereof that may contain a hetero atom consisting of an oxygen atom, a sulfur atom or a nitrogen atom. An alkylene group, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, and a divalent substituted silyl group included in the main chain. When X is a divalent atom, X is an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus atom that may have a bond with another atom. is there. X may be bonded to any substitutable carbon atom in the naphthalene ring to which they are bonded. )
(B) As a component, a polythiol compound,
(C) As a component, radical photopolymerization initiator,
As the component (D), a polyene compound that is other than dinaphthothiophene and has fewer carbon atoms than the component (A),
The content ratio of the component (A) is in the range of 5 to 50 parts by mass with respect to the total amount of the composition, and the content ratio of the component (B) is 10 to 60 masses with respect to the total amount of the composition. The resin composition for a coating material, wherein the content ratio of the component (D) is in the range of 5 to 85 parts by mass with respect to the total amount of the composition.   Furthermore, the resin composition for coating | covering materials of Claim 1 which contains a polymerization inhibitor as (E) component.   The polymerizable functional group of the component (A) is one or more members selected from the group consisting of a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, or a (meth) acrylonitrile group. The resin composition for coating | covering materials of Claim 1 or Claim 2 which exists.   The polymerizable functional group of said (A) component is an allyl ether group, The resin composition for coating | covering materials of any one of Claims 1-3 characterized by the above-mentioned.   In the said General formula (1), it is a = b = 0 and is c = d = 1, The resin composition for coating | covering materials of any one of Claims 1-4.   The said (A) component is a resin composition for coating | covering materials of any one of Claims 1-5 containing 2, 12- diallyl ether dinaphthothiophene.   The said (D) component is a resin composition for coating | covering materials of any one of Claims 1-6 whose carbon number is 6-23.   The said (D) component contains 1 or more types in the group which consists of a (meth) acrylate, an allyl compound, and an allyl ether compound, The resin composition for coating | covering materials of any one of Claims 1-7. .   The said (D) component is a resin composition for coating | covering materials of any one of Claims 1-8 containing triallyl isocyanurate.   The said (B) component is a resin composition for coating | covering materials of any one of Claims 1-9 containing 1, 8- dimercapto-3, 6- dioxaoctane.   A covering material comprising the resin composition for a covering material according to any one of claims 1 to 10.   A base material on which the coating material according to claim 11 is formed.   After forming the layer which consists of the resin composition for coating | covering materials of any one of Claims 1-10 on a board | substrate, the layer which has a refractive index lower than the said resin composition for coating | covering materials is formed. A film characterized by being formed.   A substrate having the film according to claim 13.   The element which has a base material of Claim 14.