JP2019183137A - Polymerizable composition containing inorganic oxide particle or siloxane compound, manufacturing method of layer using the polymerizable composition, and layer containing inorganic oxide particle or siloxane compound - Google Patents

Abstract

A polymerizable composition which has a single-layer structure, has a high refractive index, and is capable of forming a layer such as a sealing layer having excellent transparency. A (meth) acrylate monomer serving as a matrix resin and inorganic oxide particles or a siloxane compound coated or chemically modified with a compound having at least a (meth) acrylic group are provided. The polymerizable composition is characterized in that the difference in HSP value between the inorganic oxide particles and the compound that coats or chemically modifies the siloxane compound is 3 or more, and the viscosity at 25 ° C. is 40 mPa · s or less. [Selection diagram] None

Description

  The present invention relates to a polymerizable composition containing inorganic oxide particles or a siloxane compound, a method for producing a layer using the polymerizable composition, and a layer containing inorganic oxide particles. In particular, the present invention relates to a polymerizable composition containing inorganic oxide particles or a siloxane compound used for optical applications, a method for producing a layer using the polymerizable composition, and a layer containing inorganic oxide particles or a siloxane compound.

Resin materials used for sealing layers of optical applications, particularly liquid crystal displays, organic EL displays, touch panels using these, and the like are required to adjust the refractive index according to the layer used.
When the refractive index difference with the transparent inorganic material constituting these displays is large, the light extraction efficiency is reduced by reflection at the interface. Moreover, in a display device equipped with a touch panel that has been increasing in recent years, for example, it is transparent from the viewing side due to the influence of internal reflection of incident light at the interface with patterned ITO (indium tin oxide). The problem of “pattern appearance” that the electrode pattern is visible has been pointed out. Therefore, a high refractive index material is required to match the refractive index with the transparent inorganic material as much as possible.
On the other hand, low refractive index materials are also required for use in antireflection layers and light extraction improving layers that reduce reflection by scattering light that has passed through.

  Although there is a method of adjusting the refractive index by introducing a structure having a high or low molecular refractive index into the resin material itself, the material becomes expensive. For example, as a technique for increasing the refractive index, usually, an inorganic transparent particle having a refractive index close to that of a transparent inorganic material, for example, inorganic oxide particles is mixed with a resin material to increase the refractive index.

  As a polymerizable composition containing inorganic oxide particles, for example, in Patent Document 1, as a resin composition for hard coat, (α) an inorganic material coated with a coating material containing at least a (meth) acrylic group Oxide fine particles, (β) a cyclic monofunctional compound having a cyclic structure and having one polymerizable unsaturated group, and (γ) a polyfunctional compound having at least two polymerizable unsaturated groups, An inorganic oxide fine particle-containing composition characterized by containing

  Patent Document 2 discloses that the pressure-sensitive adhesive layer is optically formed by forming a refractive index adjustment section having a higher refractive index than the base material of the pressure-sensitive adhesive layer over a certain range in the thickness direction from the surface of the pressure-sensitive adhesive layer. It is disclosed that when used for joining members, internal reflection in a laminate formed by these optical members can be suppressed. The refractive index adjustment section having a high refractive index is configured by dispersing particles of a high refractive index material having a higher refractive index than the adhesive material in the same adhesive material as the adhesive base material.

JP 2010-85937 A JP 2017-26826 A

  A resin composition having a high refractive index can be realized by adding inorganic oxide particles having a high refractive index. However, it is necessary to use a large amount of inorganic oxide particles, which is expensive. In applications where high transparency is required, transparency may be reduced by the addition of inorganic oxide particles. In particular, when more inorganic oxide particles are added to increase the refractive index, the formed layer becomes cloudy and the visibility is lowered. Furthermore, the addition of a large amount of inorganic oxide particles increases the viscosity, which imposes restrictions on the coating method such as loss of adaptability to the inkjet process.

  Like patent document 2, the haze value of the whole adhesive layer can be restrained low by setting it as a laminated structure. However, the number of processes is increased for the laminated structure, and the manufacturing time and manufacturing cost are increased.

An object of the present invention is to provide a polymerizable composition that can be formed by an easy process, has a single layer structure, exhibits a high refractive index, and can form a layer such as a sealing layer having excellent transparency. And Another object of the present invention is to provide a layer using the polymerizable composition and a method for producing the layer.
Another object of the present invention is to provide a polymerizable composition that can be formed by an easy process, has a single layer structure, and has a vapor deposition resistance that allows the film to withstand a subsequent vapor deposition process. The polymerizable composition has low dielectric performance that suppresses malfunction of the touch panel, and enables formation of a layer such as a transparent sealing layer.

  The polymerizable composition according to the present invention includes a (meth) acrylate monomer that serves as a matrix resin, and inorganic oxide particles or a siloxane compound that is coated or chemically modified with a compound having at least a (meth) acryl group, Difference in HSP value between (meth) acrylate monomer and compound covering or chemically modifying inorganic oxide particles or siloxane compound: ΔHSP is 3 or more and viscosity at 25 ° C. is 40 mPa · s or less .

  The layer according to the present invention comprises a (meth) acrylate polymer and inorganic oxide particles or siloxane compounds coated or chemically modified with a compound having at least a (meth) acryl group, and the inorganic oxide particles or siloxane The compound is unevenly distributed on the surface of one of the layers, and the (meth) acrylate polymer and the compound having a (meth) acryl group that coats or chemically modifies the inorganic oxide particles or the siloxane compound are cross-linked. It is characterized by.

  Furthermore, the layer forming method according to the present invention includes a step of coating the polymerizable composition on a substrate to form a coating film, and a step of crosslinking and curing the coating film.

The polymerizable composition according to the present invention can segregate inorganic oxide particles or siloxane compounds to one surface side, and the layer obtained by crosslinking and curing the polymerizable composition is the surface of one layer of the layer. It can be a layer in which inorganic oxide particles or siloxane compounds are unevenly distributed. By unevenly distributing inorganic oxide particles or siloxane compounds with a dispersed particle size or domain size that does not cause visible light scattering, even if the addition amount of inorganic oxide particles or siloxane compounds is small, the refractive index can be adjusted (high refractive index) Or a layer having excellent transparency can be formed.
In addition, by forming a layer in which inorganic oxide fine particles or a siloxane compound is segregated on one surface of the layer as described above, the surface hardness is suppressed while suppressing an increase in dielectric constant compared to a uniform dispersion system. It is possible to improve the film durability when it is later subjected to a vapor deposition process such as CVD (chemical vapor deposition).

  The polymerizable composition according to the present invention is coated or chemically modified with a (meth) acrylate monomer serving as a matrix resin (hereinafter sometimes referred to as “component A”) and at least a compound having a (meth) acrylic group. , Inorganic oxide particles or siloxane compounds (hereinafter sometimes referred to as “component B”). The difference in HSP value between the (meth) acrylate monomer and the compound that coats or chemically modifies the inorganic oxide particles or the siloxane compound is 3 or more, and the viscosity of the composition at 25 ° C. is 40 mPa · s or less. It is characterized by being.

  In the present specification, the terms “(meth) acrylate” and “(meth) acryl” mean both “methacrylate” and “acrylate”, and the latter means both “methacryl” and “acryl”.

[Component A]
The (meth) acrylate monomer used as the matrix resin includes monofunctional (meth) acrylates and polyfunctional (meth) acrylates, and has a dense cross-linking structure with a compound having a (meth) acrylic group as a coating material. In order to form, it is preferable to include at least one polyfunctional (meth) acrylate. Moreover, it is preferable that it is a mixture of monofunctional (meth) acrylates and polyfunctional (meth) acrylates. From the viewpoint of lowering the viscosity of the composition, it is preferable to include a larger amount of monofunctional (meth) acrylates having a lower molecular weight. Moreover, the monomer containing a cyclic structure is preferable at the point which can improve the refractive index of hardened | cured material and can provide mechanical strength.

As monofunctional (meth) acrylates,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, Isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, Isododecyl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, Propyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, cyclodecyl (meth) acrylate, Isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane dimethanol acrylate, ethoxylated-o-phenylphenol acrylate, 2-hydroxy-o-phenylphenol propyl acrylate, methoxypolyethylene glycol (meta ) Acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) Acrylate, polypropylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-o-phenylphenolpropyl acrylate, 2- (meth) acryloyloxy Ethyl succinic acid, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl hydrophthalic acid Acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, etc. benzyl (meth) acrylate, benzyl (meth) acrylate, phenoxy Siethyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-naphthyl (meth) acrylate, 9-anthracenyl (meth) acrylate, 1-pyrenylmethyl (meth) acrylate, benzyl (meth) acrylate, tricyclodecane dimethanol mono Examples include acrylate monocarboxylic acid and dicyclopentanyl acrylate.
From the viewpoint of flexibility, a monomer having a glass transition temperature of the homopolymer of 50 ° C. or lower is preferable, a monomer of 30 ° C. or lower is more preferable, and a monomer of 10 ° C. or lower is still more preferable. Among the above, specifically, butyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate and the like are preferable.
From the viewpoint of low dielectric constant, a material having a larger (meth) acrylic group functional group equivalent (g / eq) is preferable, preferably 200 (g / eq) or more, more preferably 250 (g / eq) or more. More preferably, it is (meth) acrylate of 300 (g / eq) or more. Specifically, lauryl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, tetradecyl (meth) ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-naphthyl (meth) acrylate, 9-anthracenyl (meth) acrylate, 1-pyrenylmethyl (meth) acrylate, tricyclo Particularly preferred are decanedimethanol monoacrylate monocarboxylic acid, dicyclopentanyl acrylate and the like.
From the viewpoint of vapor deposition resistance, 2-naphthyl (meth) acrylate, 9-anthracenyl (meth) acrylate, 1-pyrenylmethyl (meth) acrylate, benzyl (meth) acrylate, tricyclodecane dimethanol monoacrylate monocarboxylic acid, dicyclo Pentanyl acrylate and the like are preferable.

As polyfunctional (meth) acrylate,
1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, isononanediol di (meth) ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange (meth) acrylate, isobornyl di (meth) acrylate, 2-hydroxy-3- ( (Meth) acrylpropyl di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate, dioxane glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate , Propoxylated ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerol tri (meth) ) Acrylate, propoxylated glycerin tri (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, bis (2 (Meth) acryloxyethyl) isocyanurate, tris (2- (meth) acryloxyethyl) isocyanurate, caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (Meth) acrylate, ditrimethylolpropane tetraacrylate, ethoxylated ditrimethylolpropane tetraacrylate, propoxy Ditrimethylolpropane tetraacrylate, dipentaerythritol poly (meth) acrylate, ethoxylated dipentaerythritol poly (meth) acrylate, propoxylated dipentaerythritol poly (meth) acrylate, dendritic polymer poly (meth) acrylate, ethoxylated poly Reaction product of glycerin poly (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and acrylic acid (manufactured by Shin-Nakamura Kogyo Co., Ltd., Trade name "NK ester A-BPEF") and the like.
Among these, from the viewpoint of increasing the refractive index, a reaction product of tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and acrylic acid (Shin Nakamura) Kogyo Co., Ltd., trade name "NK ester A-BPEF") is preferred. From the viewpoint of flexibility, 1,10-decanediol di (meth) acrylate is preferable.
From the viewpoint of low dielectric constant, reaction product of tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and acrylic acid (Shin Nakamura Kogyo Co., Ltd.) Manufactured, trade name “NK Ester A-BPEF”), 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate.

[B component]
“Coating” is a state in which a coating material is physically or electrostatically coated on the surface of inorganic oxide particles or the like, and “chemical modification” is a function of the surface of inorganic oxide particles or the like. A state in which a group (such as an OH group) and a functional group of the coating material are reacted and bonded.
The inorganic oxide particles are preferably nanoparticles containing at least one inorganic metal oxide selected from titanium oxide (titania), zirconium oxide (zirconia), zinc oxide, niobium oxide, and silica (silicon dioxide). Among these, titania and / or zirconia is more preferable from the viewpoint of refractive index, and zirconia is most preferable.
The inorganic oxide may be a porous fine particle, and is preferably a porous fine particle when a low refractive index or a low dielectric constant is required.

  The particle diameter of the inorganic oxide particles is a nano-level particle diameter, preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. If it is below the upper limit, the transparency tends not to be impaired. On the other hand, the lower limit of the particle diameter is 1 nm or more, preferably 2 nm or more. The particle diameter refers to a particle diameter obtained by image analysis when morphological observation is performed with a field emission scanning electron microscope (FE-SEM), a transmission electron microscope (TEM), or the like.

The siloxane compound may be any compound as long as it has a siloxane bond, but is preferably silsesquioxane represented by [RSiO _3/2 ] _n or a derivative thereof. Examples of R include an alkyl group such as a methyl group and a cyclohexyl group, an aryl group such as a phenyl group, an alkenyl group such as a vinyl group, an alkoxy group such as a methoxy group and a phenoxy group, and a halogen such as chlorine. RSiO _3/2 is called a T unit, and the R for each T unit may be the same or different. Examples of the derivative include those in which the hydrocarbon group of R is substituted with halogen or the like. The structure of silsesquioxane may be any form such as a random structure, a ladder structure, or a cage structure. Mixtures of these structures can also be used.

The siloxane compound may have any shape from a relatively low molecular weight amorphous material to a high molecular weight nanoparticle type, but a high molecular weight nanoparticle type is preferred.
It is preferable to use a nanoparticle type siloxane compound (silsesquioxane) having the same particle diameter as that of the inorganic oxide particles.

In the B component used in the present invention, the inorganic oxide particles or the siloxane compound is coated or chemically modified with a compound having at least a (meth) acryl group. In addition, the coating material or the chemical modifying material that is a compound that coats or chemically modifies the inorganic oxide particles or the siloxane compound includes a compound having a difference in HSP value of 3 or more from the (meth) acrylate monomer serving as the matrix resin. The difference in HSP value is more preferably 4 or more, more preferably 5 or more, more preferably 6 or more, more preferably 7 or more, and still more preferably 8 or more, Most preferably, it is 9 or more. The upper limit is 12 or less. When ΔHSP is equal to or greater than the above lower limit, the driving force for the inorganic oxide particles to be unevenly distributed on the surface of any one of the layers is obtained. Further, when the ΔHSP value is not more than the upper limit, aggregation of the B component is suppressed and the dispersion tends to be good.
In addition, when the inorganic oxide particle or the siloxane compound is coated or chemically modified with a plurality of compounds, at least one of the compound having a (meth) acrylic group and the other coating material or chemical modifying material is the HSP. It is sufficient to satisfy the difference in values.
Preferably, all of the coating material or the chemical modifier satisfy the difference in the HSP value.

The HSP value in the present invention is a Hansen solubility parameter that takes into account the polarity of a substance divided into three components: a dispersion force term (δ _D ), a polar force term (δ _P ), and a hydrogen bonding force term (δ _H ). is there. In the case of multiple components, the total value can be set according to the component ratio. The difference in the HSP value (ΔHSP) in the present invention is represented by the following formula. Here, for the two components, component A and component B, the terms are represented by δ _DA , δ _PA , δ _HA and δ _DB , δ _PB , δ _HB .
ΔHSP = {4 (δ _DA -δ _DB ) ² + (δ _PA -δ _PB ) ² + (δ _HA -δ _HB ) ² } ^1/2

  Those having a small difference are compatible. When the difference is large, the compatibility is lowered and phase separation is likely to occur.

  Thus, B component floats or sinks in a composition by there being a difference in HSP value. When the (meth) acrylate of the matrix resin is polymerized in that state, it is cross-linked with the compound having a (meth) acrylic group of the coating material or chemical modifier, and the B component is fixed in a segregated state. By making the difference in HSP value and the content of the B component within a specific range, the B component can be made into a particle dispersion and domain state of a size that does not cause visible light scattering, and both segregation and transparency are achieved. Layer formation is possible.

Specific examples of the compound having a (meth) acrylic group as a coating material or a chemical modifier include methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2- Examples thereof include unsaturated carboxylic acids such as methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-acryloyloxyethyl phthalic acid. Further, silylated products of these unsaturated carboxylic acids, particularly compounds modified with alkoxysilanes can also be used. For example, silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Compounds.
In addition, as a coating material or a chemical modifier, a linear carboxylic acid such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, stearic acid; 2-ethylhexanoic acid, Branched carboxylic acids such as 2-methylheptanoic acid, 4-methyloxanoic acid and neodecanoic acid; cyclic carboxylic acids such as naphthenic acid and cyclohexanedicarboxylic acid can be used. Of these, branched carboxylic acids such as neodecanoic acid and 2-ethylhexanoic acid are preferred.

The ratio of the inorganic oxide particles or siloxane compound to the coating material or chemical modifier is preferably 60% by mass or more for inorganic oxide particles or siloxane compound (that is, 40% by mass or less for coating material). It is preferable that object particle | grains or a siloxane compound is 95 mass% or less (namely, coating | covering material is 5 mass% or more). The amount of the coating material or the chemical modifier is more preferably 10 to 30% by mass.
In the case of inorganic oxide particles that have been coated or chemically modified, the amount of the coating material or chemically modified material is determined using a method such as TG-DTA (thermogravimetric-suggested thermal analysis) in an air atmosphere. It can be expressed as a weight loss rate when the organic component is removed by heating to 800 ° C.

  A known method can be used for coating or chemical modification of the inorganic oxide particles, and the surface of the inorganic oxide particles is modified by dropping a coating material into the dispersion of the inorganic oxide particles, as in various coupling treatments. be able to. Alternatively, a metal oxide precursor compound and a coating material may be mixed with water, and metal oxide particles coated or chemically modified with the coating material may be obtained by hydrothermal synthesis.

The content of the inorganic oxide particles or the siloxane compound is preferably 60% by mass or less based on the total amount of the composition. More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less, Especially preferably, it is 45 mass%. Moreover, Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. In addition, content of an inorganic oxide particle or a siloxane compound is an amount which does not contain a coating material or a chemical modifier. When the content of the inorganic oxide particles or the siloxane compound is not more than the above upper limit value, the viscosity of the polymerizable composition does not become too high and tends to be segregated. Moreover, it exists in the tendency for the effect by segregation to be acquired because it is more than the said lower limit.
The content of the inorganic oxide particles or the siloxane compound is preferably 18 vol% or less, more preferably 16 vol% or less, and more preferably 15 vol% or less in the total volume of the composition in terms of volume fraction from the viewpoint of suppressing the viscosity. More preferably, it is more preferably 13 vol% or less, and particularly preferably 10 vol% or less.

<Polymerization initiator>
The polymerizable composition of the present invention preferably contains a polymerization initiator. As the polymerization initiator, a polymerization initiator that generates radical, cation or anion active species by light or heat can be used. From the viewpoint of reducing member damage, a photopolymerization initiator or a combined use with a photopolymerization initiator and a thermal polymerization initiator is preferred.

(Photopolymerization initiator)
A known compound can be used as the photopolymerization initiator. For example, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4 , 6-Trimethylbenzoyl) phenylphosphine oxide, benzoyls such as diethoxyacetophenone;
Benzoins such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one;
α-aminoalkylphenones,
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Photo radical initiators such as oxime esters such as -yl]-, 1- (O-acetyloxime); Moreover, the salt represented by A ^<+> B ^{< - >} which generate | occur | produces a cation active species by light irradiation is mentioned. Here, the cation A ⁺ is preferably an aromatic iodonium ion or an aromatic sulfonium ion.
Further, the anion B ^- _is, ^SbF 6 -, PF ₆ ^- or _{B (C 6 F 5) 4} - , such as, B _{(aryl) 4} ^- preferably comprises at least an initiator which is an ion. Examples of B (aryl) ₄ ⁻ include photocations such as B (C ₆ F ₄ OCF ₃ ) ₄ ⁻ and B (C ₆ F ₄ CF ₃ ) ₄ ⁻ in addition to B (C ₆ F ₅ ) ₄ ^—. Initiators are mentioned.
Among these, from the viewpoint of curability, benzoins, benzoyls, and oxime esters are preferable, and in particular, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,4,6 -Trimethylbenzoyl) phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is preferred. These photopolymerization initiators may be used alone or in combination of two or more.

  A photoinitiator is 0.001 mass part or more normally when the polymerizable composition of this invention is 100 mass parts, Preferably it is 0.02 mass part or more, More preferably, it is 0.05 mass part or more. The upper limit is usually 10 parts by mass or less, preferably 9 parts by mass or less, and more preferably 6 parts by mass or less. When the addition amount of the photopolymerization initiator is not more than the above upper limit, the polymerization does not proceed rapidly, and the birefringence of the cured product tends to be lowered and the hue can be improved. On the other hand, it exists in the tendency for a polymeric composition to fully superpose | polymerize because it is more than the said minimum.

(Thermal polymerization initiator)
Known compounds can be used as the thermal polymerization initiator. For example, a hydroperoxide in which one hydrogen atom such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide is substituted with a hydrocarbon group oxide;
Dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, 1,1-di (t-hexylperoxy) cyclohexane;
peroxyesters such as t-butylperoxybenzoate, t-butylperoxy (2-ethylhexanoate);
Diacyl peroxides such as benzoyl peroxide and dilauroyl peroxide; peroxycarbonates such as diisopropyl peroxycarbonate; peroxides such as peroxyketal and ketone peroxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy -2,4-dimethylvaleronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2'-azobis (2-methylpropionate), 1,1'-azobis (1- And thermal radical initiators such as azo compound-based initiators such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile);

A thermal cation initiator that generates a cationically active species by heat can also be used. This is a compound that cannot generate a practical amount of a cationically active species by light irradiation, and is a salt represented by the above A ⁺ B ⁻ . The temperature at which the cationic active species is generated is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. Moreover, it is preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
Here, the cation A ⁺ is preferably a sulfonium ion (SR ₃ ⁺ ) containing a sulfur atom (S), and more preferably a sulfonium ion in which at least one of the three R groups bonded to S is an alkyl group. In this case, two groups may be combined to form an alkylene group and form a ring with S. The remaining group is preferably a thermal cation initiator such as an aryl group which may have a substituent, an alkyl group which may be substituted with an aryl group, or an alkenyl group. Examples of the anion B ⁻ include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like.
Examples of the thermal cation initiator include benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate and diphenyl (methyl) sulfonium tetrafluoroborate.

  Among the thermal polymerization initiators, dialkyl peroxides, diacyl peroxides, peroxy esters, hydroperoxides, or azo compound-based initiators are preferable from the viewpoint of polymerizability. More specifically, dicumyl peroxide, di-t-butyl peroxide, 1,1-di (t-hexylperoxy) cyclohexane, dilauroyl peroxide, t-butylperoxybenzoate, t-butyl hydroperoxide 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and the like are preferable. These polymerization initiators may be used alone or in combination of two or more.

  The thermal polymerization initiator is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more when the polymerizable composition of the present invention is 100 parts by mass. The upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less. When the thermal polymerization initiator is not more than the above upper limit, after photopolymerizing the polymerizable composition, the polymerization at the time of demolding and thermal polymerization does not proceed rapidly, and the birefringence of the cured body is reduced, There is a tendency to improve the hue. On the other hand, it is in the tendency for thermal polymerization to fully advance because it is more than the above-mentioned minimum.

  When the photopolymerization initiator and the thermal polymerization initiator are used in combination, the mass ratio is usually “100: 1” to “1: 100” (“photopolymerization initiator: thermal polymerization initiator”, hereinafter, in this paragraph) Similarly, it is preferably “10: 1” to “1:10”. It exists in the tendency for superposition | polymerization to become sufficient because a thermal-polymerization initiator is more than the said minimum, and it exists in the tendency which suppresses coloring by being below the said upper limit.

When the viscosity of the polymerizable composition of the present invention is smaller, segregation of the B component occurs more smoothly, and application to an inkjet process or the like becomes possible, and options for a coating method using the polymerizable composition are expanded. Therefore, it is preferable.
The polymerizable composition of the present invention has a viscosity at 25 ° C. of 40 mPa · s or less, preferably 30 mPa · s or less, more preferably 20 mPa · s or less, and even more preferably 10 mPa · s or less. The viscosity may be appropriately adjusted according to the type and combination of monomers used, the amount of inorganic oxide particles added, and the amount of polymerization initiator added. The viscosity is a value measured using a B-type viscometer under the condition of a temperature of 25 ° C. When a solvent is included, the viscosity is a value measured by removing the solvent with an evaporator or the like.

  The polymerizable composition of the present invention uses a (meth) acrylate monomer as a self-solvent, and is preferably substantially free of other solvents. However, it does not prevent the solvent contained in the dispersion of inorganic oxide particles from being accompanied.

[layer]
The layer according to the present invention includes a (meth) acrylate polymer and inorganic oxide particles or a silsesquioxane compound coated or chemically modified with a compound having at least a (meth) acryl group. A compound having a (meth) acryl group in which the inorganic oxide particles or siloxane compound is unevenly distributed on the surface of any one of the layers, and the inorganic oxide particles or siloxane compound is coated or chemically modified; The (meth) acrylate polymer is crosslinked.
The (meth) acrylate polymer, inorganic oxide particles or silsesquioxane compound coated or chemically modified with a compound having at least a (meth) acryl group, are used in the polymerization composition. It is synonymous with inorganic oxide particle | grains or a silsesquioxane compound coat | covered or chemically modified with the compound and the compound which has a (meth) acryl group at least.

  Although the formation method of the layer concerning this invention is not specifically limited, It can form by apply | coating the polymeric composition concerning this invention on a base material, forming a coating film, and polymerizing and hardening this coating film. Alternatively, it may be formed by a method of coating on a support different from the substrate, polymerizing and curing, and then transferring it onto the substrate. When the polymerizable composition is applied onto the substrate, it is applied so as to have a uniform film thickness by a method such as spin coating or an inkjet method. Moreover, after forming a coating film, after leaving still for a predetermined time until the segregation of B component is completed, a coating film is polymerized and hardened. The standing time varies depending on the composition and viscosity of the polymerizable composition, the particle diameter of the inorganic oxide particles, etc., but is generally preferably 5 seconds or more, and more preferably 30 seconds or more.

  As described above, the polymerization curing is preferably performed by a photocuring reaction or a combination of photocuring and heat curing. Usually, photocuring reaction is performed by irradiating light containing ultraviolet rays (UV). Irradiation with UV light may be performed in any way as long as it does not affect the substrate and other members. The irradiation amount and the irradiation time are appropriately adjusted so that the polymerization curing (crosslinking) is sufficiently completed. The polymerization may be performed in the atmosphere (in the air) or in an inert gas such as a nitrogen atmosphere. From the viewpoint of increasing the degree of segregation by reaction-induced phase separation, it is more preferable to carry out in an inert gas, for example, a nitrogen atmosphere.

  By such a method, the B component is unevenly distributed on the surface of any one of the layers, and the compound having a (meth) acryl group that coats or chemically modifies the inorganic oxide particles or the siloxane compound. A layer in which the (meth) acrylate polymer is crosslinked can be obtained.

  The thickness of the layer can be appropriately changed according to the purpose, but when used for a sealing layer of an input / output device or the like, it is usually 5 μm to 500 μm, and more preferably 5 μm to 400 μm from the viewpoint of reducing the thickness of the device. More preferably 5 μm to 300 μm, more preferably 5 μm to 200 μm, further preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, still more preferably 5 μm to 20 μm, particularly preferably 5 μm to 10 μm. It is.

  The degree of uneven distribution of the B component (also referred to as uneven distribution) is a peak derived from an inorganic oxide or siloxane compound in the ATR measurement of the surface (front surface) of one layer where the B component is unevenly distributed and the surface (back surface) of the other layer. It can be expressed by the front / back ratio of the integrated value. If this surface / back surface ratio (degree of uneven distribution) is larger than 1, it can be said that the amount of the surface of the inorganic oxide particles or the siloxane compound is different from the amount of the back surface. In the present invention, this surface / back surface ratio is 1.5 or more. Some cases are ubiquitous. The degree of uneven distribution is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 5 or more, and most preferably 6 or more. The upper limit of the degree of uneven distribution achieved by the present invention is up to about 10.

The layer according to the present invention has high transparency, and the refractive index is adjusted to be higher or lower than the refractive index of the matrix resin. For example, when adding inorganic oxide particles having a refractive index sufficiently higher than that of the matrix resin, the amount of the inorganic oxide particles, the matrix resin, the coating material or the chemicals are adjusted so that the refractive index of the layer is 1.65 or more. It is preferable to adjust the type and composition of the modifier.
The refractive index is the refractive index (n _D ) at the D line (wavelength 589 nm). In the layer according to the present invention, the refractive index n _D is more preferably 1.70 or more, more preferably 1.73 or more, and further preferably 1.76 or more. In addition, the refractive index of a normal acrylic resin is about 1.47.
On the other hand, the siloxane compound is lower than the refractive index of the acrylic resin, and can lower the refractive index of the cured product layer of the composition.

The content of the inorganic oxide particles or the siloxane compound in the layer is preferably 60% by mass or less in the layer. More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less, Especially preferably, it is 45 mass%. Moreover, Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. In addition, content of an inorganic oxide particle or a siloxane compound is an amount which does not contain a coating material or a chemical modifier. It exists in the tendency for the effect by segregation to be acquired because content of an inorganic oxide particle or a siloxane compound is the said range.
The content of the inorganic oxide particles or the siloxane compound is preferably 19 vol% or less, more preferably 17 vol% or less, and more preferably 16 vol% or less in the volume fraction in terms of volume fraction because an effect due to segregation is obtained. More preferably, it is more preferably 14 vol% or less, and particularly preferably 11 vol% or less.

[Other additives]
The polymerizable composition of the present invention is a monomer or resin component other than inorganic oxide particles or a siloxane compound, which is coated or chemically modified with a (meth) acrylate monomer to be a matrix resin and a compound having at least a (meth) acryl group. , Tackifier resin, softener, solvent, corrosion inhibitor, heat stabilizer, ultraviolet absorber, infrared absorber, colorant, antioxidant, antifungal agent, pH adjuster, flame retardant, crystal nucleating agent, conductivity Particles, inorganic particles, organic particles, viscosity modifiers, lubricants, surface treatment agents, leveling agents, crosslinking agents, antifoaming agents, sensitizers, and various components may be included for the purpose of providing further functions. The solvent is preferably not contained in terms of process efficiency.

(Amount of other additives)
The content of the other additives in the polymerizable composition is not particularly limited as long as the effects of the present invention are not significantly impaired. When the polymerizable composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely with reference to an Example, this invention is not limited only to these Examples.

<Preparation of acrylic monomer polymerization liquid (1)>
As monofunctional (meth) acrylate, 53.4 g of normal butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and as polyfunctional (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and acrylic acid Reaction product (made by Shin-Nakamura Kogyo Co., Ltd., trade name “NK Ester A-BPEF”) 5.4 g, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF, as photopolymerization initiator) 1.2 g of trade name “Irgacure 819”) was weighed and mixed using a mix rotor to obtain an acrylic monomer polymerization liquid (1).

<Preparation of acrylic monomer polymerization liquid (2)>
Except for changing the photopolymerization initiator to 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, trade name “Irgacure TPO”), the same procedure as in the acrylic monomer polymerization liquid (1) was performed. ) Was prepared.

<Preparation of acrylic monomer polymerization liquid (3)>
Acrylic monomer polymerization solution except that monofunctional (meth) acrylate is changed to isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and photopolymerization initiator is changed to 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name “Irgacure 184”). In the same manner as in (1), an acrylic monomer polymerization liquid (3) was prepared.

<Preparation of acrylic monomer polymerization liquid (4)>
An acrylic monomer polymerization liquid (4) was prepared in the same manner as the acrylic monomer polymerization liquid (3) except that the monofunctional (meth) acrylate was changed to 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

<Preparation of acrylic monomer polymerization liquid (5)>
As monofunctional (meth) acrylate, 35.0 g of isostearyl acrylate and 11.7 g of dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-513AS”), 1,10 as polyfunctional (meth) acrylate -Decanediol diacrylate (manufactured by Shin-Nakamura Kogyo Co., Ltd., trade name “A-DOD-N”) 2.2 g, polymerization initiator 1-hydroxycyclohexyl phenyl ketone (BASF, trade name “Irgacure 184”) 1.0 g An acrylic monomer polymerization liquid (5) was prepared in the same manner as in the acrylic monomer polymerization liquid (4) except for changing to.

<Preparation of coated zirconia dispersion>
Pure water (268 g) was mixed with 2-ethylhexanoic acid zirconium mineral spirit solution (Daiichi Rare Element Chemical Co., Ltd.) (782 g). The mixture was charged into an autoclave equipped with a stirrer, and the atmosphere in the reaction vessel was replaced with nitrogen gas. Thereafter, the reaction solution was heated to 180 ° C. and reacted for 16 hours to synthesize zirconium oxide. The pressure in the container when reacted at 180 ° C. was 1.03 MPa.
The solution after the reaction was taken out, the precipitate accumulated at the bottom was filtered off, washed with acetone and dried. When the precipitate (100 g) after drying was dispersed in toluene (800 mL), a cloudy solution was obtained.
Next, it filtered again with the quantitative filter paper (Advantech Toyo Co., Ltd. No.5C) as a refinement | purification process, and removed the coarse particle etc. in a deposit. Next, white zirconium oxide nanoparticles were recovered by removing toluene obtained by concentrating the filtrate under reduced pressure.
The zirconium oxide nanoparticles (10 g) obtained above were dispersed in toluene (90 g) to obtain a transparent dispersion. To the dispersion, 3-methacryloxypropyltrimethoxysilane (1.5 g, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was added as a surface treatment agent, and the mixture was heated to reflux at 90 ° C. for 1 hour. Next, n-hexane was added to the dispersion after the reflux treatment to aggregate the dispersed particles, thereby making the dispersion cloudy. Aggregated particles were separated from the white turbid solution using a filter paper, and then heated and dried at room temperature to prepare zirconium oxide nanoparticles surface-treated with 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane.
When the particle diameter of the obtained coated zirconium oxide nanoparticles was measured by FE-SEM, the average particle diameter was 12 nm. Furthermore, when analyzed by an infrared absorption spectrum, absorption derived from Si—O—C was observed in addition to absorption derived from C—H and absorption derived from COOH. These absorptions are considered to originate from 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane covering the zirconium oxide nanoparticles. In addition, when the mass reduction rate of the zirconium oxide nanoparticles when the temperature was increased to 800 ° C. at a rate of 10 ° C./min in an air atmosphere by TG-DTA (thermogravimetric-suggested thermal analysis), 18 mass% Decrease rate. Therefore, it was confirmed that 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane covering the zirconium oxide nanoparticles were 18% by mass of the whole particles.
20% by mass of phenoxybenzyl acrylate is added to 80% by mass of zirconium oxide nanoparticles surface-treated with 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane obtained above, and the mixture is oxidized by stirring. A monomer dispersion containing 80% by mass of zirconia nanoparticles was obtained.
Examples 1-4 and Comparative Examples 1-2 used this coated zirconia dispersion.
In Example 5, a 50 mass% ethyl acetate dispersion of zirconia oxide particles coated with a coating material having an HSP value of δD = 19.91, δP = 8.36, δH = 8.69 was used. The particle diameter of the coated zirconium oxide particles by TEM observation was 5 nm.

<Example 1>
(Preparation of coated zirconia-containing polymerizable composition)
2.6 g of acrylic monomer polymerization liquid (1) and 4.4 g of coated zirconia dispersion are weighed and mixed for 5 minutes with a kneader (Shinky, trade name “Awatori Netaro (AR-250)”) After 1 minute, a coated zirconia-containing polymerizable composition (1) was obtained.

Coated zirconia dispersion: coated zirconia concentration 80 mass%, zirconia / coating material = 82/18 (mass ratio),
It calculated | required as the zirconia density | concentration of the whole composition = {(4.4 * 0.8 * 0.82) / (2.6 + 4.4)} * 100 = 41 (mass%).

  The viscosity of the polymerizable composition (1) was measured at 25 ° C. using a B-type viscometer “DV-I + VISCOMETER” (trade name) manufactured by BROOK FIELD, and found to be 8 mPa · s.

(Preparation of coated sample on glass for optical evaluation)
Using a micropipettor, 1 mL of the polymerizable composition (1) was placed on a slide glass (2.5 cm × 7.5 cm, water polished, manufactured by Matsunami Glass Industrial Co., Ltd.), and a spin coater (Mikasa Co., Ltd.) 1H-D7) was applied under a rotation condition of 250 rpm · 15 s, and UV irradiation was performed in a nitrogen atmosphere to obtain a glass-coated sample for optical evaluation (film thickness: 11 μm).

UV irradiation conditions: UV irradiation of 3 J / cm ² using a UV lamp conveyor system (bulb: V type) manufactured by Fusion UV Systems Japan Co., Ltd. (currently Heraeus Co., Ltd.)

(Optical evaluation)
(Optical evaluation by spectrophotometer: refractive index calculation)
The transmittance and reflectance of D-line (589 nm) of the prepared optical evaluation glass-coated sample were measured at room temperature (25 ° C.) with a spectrophotometer (manufactured by Hitachi High-Technologies, U-4000). From the data obtained by subtracting (transmittance / reflectance), n _D (refractive index) of the coated sample on glass was calculated.

(Appearance evaluation)
The appearance (transparency) of the cured product was evaluated visually.
(Haze evaluation)
Using a TM double beam automatic haze computer HZ-2 (manufactured by Suga Test Instruments Co., Ltd.), a haze evaluation of a sample on a glass for optical evaluation was performed. At this time, the blank Haze of only the slide glass was subtracted to obtain the Haze value of the sample coated on glass.

(ATR evaluation: calculation of segregation degree data of zirconia particles)
Using the Thermo Fisher Scientific FT-IR spectrometer Nicoleti S5, infrared spectroscopic analysis (total reflection method / ATR) of the front and back surfaces of the prepared optically coated glass-on-glass sample was carried out. First, a polymer obtained by UV-curing only the acrylic monomer polymerization liquid (1), and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (made by BASF, trade name “Irgacure 819”) in the coated zirconia dispersion liquid Each ATR data was obtained with a polymer obtained by UV-curing a liquid added with 2% by mass. (UV irradiation conditions are the same as above). From the ATR data, a zirconium oxide (ZrO ₂ ) -derived peak was present at 1517 to 1576 cm ⁻¹ only in the polymer of the coated zirconia dispersion. It is possible to compare the amount ratio of zirconia by comparing the peak integration values of the above samples. By the method shown on the left, the surface / back surface ratio (degree of segregation) of the peak integrated value derived from zirconium oxide on the front surface and the back surface was 5.86, and it was found that the zirconia particles were segregated by the surface.

(Electron microscope evaluation: segregation range)
The cured sample was thinned by setting it to a thickness of 100 nm by the FIB processing method, and a high-resolution HAADF-STEM image (observation magnification: 20,000 times and 80,000) using a TECNAI G2 F20 transmission electron microscope manufactured by FEI. Times). The HAADF-STEM strength reflects the amount of zirconium oxide, but the strength is 10a. u. More than that. The depth (nm) in the thickness direction was 247-2184 (nm) from the surface, and it was found that zirconia particles were segregated in the vicinity of 2 μm on the surface.

(Calculation of HSP value)
The HSP value of the monomer was implemented using calculation software HSPiP manufactured by Pirika. The HSP value of the monomer mixture was calculated from the following equation using the mixing ratio (vol%).
[δ _Dm , δ _Pm , δ _Hm ] = [(a × δ _D1 + b × δ _D2 ), (a × δ _P1 + b × δ _P2 ), (a × δ _H1 + b × δ _H2 )] / ( a + b)
( _Where δ _Dm , δ _Pm and δ _Hm are the HPS values of the mixture, δ _D1 , δ _P1 and δ _H1 are the HPS values of the first monomer, δ _D2 , δ _P2 and δ _H2 are the HPS values of the second monomer, a represents the mixing ratio of the first monomer, and b represents the mixing ratio of the second monomer.)

Next, the ΔHSP value was calculated as follows. The HSP values of 2-ethylhexanoic acid, which is a coating material of zirconia, are δD = 16.1, δP = 4.1, δH = 8.6, and the HSP value of 3-methacryloxypropyltrimethoxysilane is δD = 14. 9, δP = 4.1, δH = 4.6. The ΔHSP value with the matrix resin (meth) acrylate monomer is calculated by the following equation: ΔHSP = 3.2 for 2-ethylhexanoic acid, ΔHSP = 2.6 for 3-methacryloxypropyltrimethoxysilane, The ΔHSP between the (meth) acrylate monomer serving as the matrix resin and 3-methacryloxypropyltrimethoxysilane, which is one component of the compound that coats the inorganic oxide zirconia, was 3 or more.
ΔHSP = {4 (δ _DA -δ _DB ) ² + (δ _PA -δ _PB ) ² + (δ _HA -δ _HB ) ² } ^1/2

<Examples 2 to 5, Comparative Examples 1 and 2>
A polymerizable composition was prepared with the composition shown in Table 1, and a glass-coated sample for optical evaluation was prepared and evaluated in the same manner as in the Examples under the polymerization atmosphere shown in Table 2. Together with the results of Example 1, Table 1 shows the evaluation of the polymerizable composition, and Table 2 shows the evaluation of the cured product.

<Example 6>
To 8.4 g of the monomer polymerization liquid (5) shown in Table 3, 3.2 g of nano colloidal silica (Y10SM-AM1, 50% MEK dispersion manufactured by Admatechs) treated with a methacryl group-containing silane coupling agent was added and kneaded. A polymerizable composition (8) was prepared by carrying out mixing for 5 minutes and defoaming for 1 minute using a machine (trade name “Awatori Nertaro (AR-250)” manufactured by Shinky Corporation). Using a micropipette, 1 mL of the polymerizable composition (8) was placed on an ITO solid substrate (50 mm × 50 mm × 0.7 mm), and 600 rpm · 30 s using a spin coater (Mikasa Co., Ltd., 1H-D7). It was applied under the following rotation conditions. Thereafter, the solvent was removed by leaving it on a hot plate at 70 ° C. for 5 minutes, and then UV irradiation was performed in a nitrogen atmosphere to obtain an on-glass sample for optical evaluation (film thickness 12 μm). At this time, since it is necessary to make an exposed ITO portion for evaluating the dielectric constant, a part of the coated surface was wiped off with a cotton swab before UV irradiation to prepare an exposed ITO portion.
The UV irradiation conditions were the same as in Example 1.

(Metal Al deposition)
In order to evaluate the dielectric constant, 4 mm x 4 mm x Al (Aluminium Metal Wire 99.99% purity manufactured by Furuuchi Chemical Co., Ltd.) was used at a rate of 1 nm / S on the sample after UV irradiation using a vacuum deposition apparatus. Vapor deposition was performed on 100 nm (thickness) × 4 spot portions.

(Dielectric constant, deposition resistance evaluation)
The dielectric constant of the sample on which the metal Al was vapor-deposited was measured in an environment of 23 ° C. and 50% RH using an LCR meter (Keyence GT2-H12KL) (frequency ranges from 100 Hz to 1000000 Hz). Regarding the vapor deposition resistance, the case where the deposited Al surface was a mirror surface was marked with ◯, and the cloudy one was marked with x.

<Example 7, Comparative Examples 3 and 4>
Each polymerizable composition was prepared with the composition shown in Table 3, and in the same manner as in Example 1, preparation of a sample after UV irradiation, metal Al vapor deposition, dielectric constant, and vapor deposition resistance were evaluated. The evaluation is shown in Table 3.
In Table 3, methacryl group-containing nanocolloidal silica is Y10SM-AM1 (solid content 50 wt%, MEK dispersion) manufactured by Admatechs, and phenyl group-containing nanocolloidal silica is Y10SP-AM1 (solid content 30.9 w%, MEK, manufactured by Admatex). The dispersion was used and blended with the polymerization solution so that the amount of nanocolloidal silica in the entire polymerizable composition after removing the solvent was the amount shown in Table 3.

The abbreviations in Tables 1 and 3 are as follows.
Monofunctional monomer nBA: normal butyl acrylate IBA: isobornyl acrylate 2EHA: 2-ethylhexyl acrylate ISA: isostearyl acrylate FA-513AS: dicyclopentanyl acrylate manufactured by Hitachi Chemical Co., Ltd.
Product Name: “FA-513AS”
A-DOD-N: Shin-Nakamura Kogyo Co., Ltd. 1,10-decanediol diacrylate
Product name "A-DOD-N"
・ Multifunctional monomer A-BPEF: Shin-Nakamura Kogyo Co., Ltd., trade name “NK Ester A-BPEF”
-Polymerization initiator 819: Product name "Irgacure 819" manufactured by BASF
TPO: BASF, trade name “Irgacure TPO”
184: BASF product name "Irgacure 184"

In Comparative Example 1, since the addition amount of zirconia particles was large and the viscosity of the polymerizable composition was increased, segregation of zirconia particles did not occur, and the refractive index was higher than that of other examples despite the large addition amount. It became low. Further, the haze deteriorated due to the large amount of zirconia particles added.
In Comparative Example 2, since a large amount of 2-ethylhexyl acrylate was used as a monofunctional monomer, zirconia aggregated to form a heterogeneous liquid, and the viscosity of the polymerization composition could not be measured. Moreover, the haze value was very high, and the whole became cloudy, and the refractive index was not measured.
On the other hand, in Examples 1 to 5, sufficient segregation of the zirconia particles occurred, and it was possible to form a layer having a high refractive index, a low haze, and excellent transparency.
In addition, Examples 6 and 7 sufficiently satisfy both the dielectric constant and the vapor deposition resistance. On the other hand, Comparative Examples 3 and 4 used nano colloidal silica treated with a phenyl group-containing silane coupling agent, and thus did not satisfy both the dielectric constant and the vapor deposition resistance.

The polymerizable composition according to the present invention can be adjusted to a refractive index sufficiently higher or lower than the refractive index of the matrix resin by adding relatively few inorganic oxide particles or a siloxane compound, and has a good deposition resistance and a dielectric constant. It is possible to provide a cured product layer that is low and excellent in transparency. As a result, a sealing layer suitable for optical applications can be provided as a single layer, which can contribute to a reduction in device cost.
The sealing layer according to the present invention is suitable for a liquid crystal display, an organic EL display, and an image input / output device such as a touch panel using these, and solves a problem of “pattern appearance” such as a transparent electrode and a touch panel malfunction. it can.

Claims (15)

  A (meth) acrylate monomer to be a matrix resin and inorganic oxide particles or siloxane compounds coated or chemically modified with a compound having at least a (meth) acryl group, the (meth) acrylate monomer and the inorganic oxide particles Alternatively, a polymerizable composition characterized in that a difference in HSP value from a compound that coats or chemically modifies a siloxane compound is 3 or more, and a viscosity at 25 ° C. is 40 mPa · s or less.   The polymerizable composition according to claim 1, wherein the (meth) acrylate monomer contains at least one polyfunctional (meth) acrylate.   The polymerizable composition according to claim 2, wherein the (meth) acrylate monomer includes one or more polyfunctional (meth) acrylates and one or more monofunctional (meth) acrylates.   The polymerizable composition according to any one of claims 1 to 3, wherein the content of the inorganic oxide particles or the siloxane compound not containing a compound to be coated or chemically modified in the polymerizable composition is 60% by mass or less.   The polymerizable composition according to any one of claims 1 to 4, wherein the inorganic oxide particles are zirconium oxide particles, and the zirconium oxide particles have a particle size of 100 nm or less.   Furthermore, the polymeric composition of any one of Claims 1-5 containing a photoinitiator.   A layer comprising (meth) acrylate polymer and inorganic oxide particles or silsesquioxane compound coated or chemically modified with a compound having at least a (meth) acryl group, the inorganic oxide particles or siloxane A compound having a (meth) acryl group and a (meth) acrylate polymer in which the compound is unevenly distributed on the surface of any one of the layers, and the inorganic oxide particles or the siloxane compound is coated or chemically modified. A layer characterized by being crosslinked.   The layer according to claim 7, wherein the content of the inorganic oxide particles or the siloxane compound not containing a compound to be coated or chemically modified in the layer is 60% by mass or less.   The layer according to claim 7 or 8, wherein the inorganic oxide particles are zirconium oxide particles, and the particle diameter of the zirconium oxide particles is 100 nm or less.   In the layer, the surface / back surface ratio of the peak integrated value derived from zirconium oxide in ATR measurement between one layer surface (front surface) where the inorganic oxide particles are unevenly distributed and the other layer surface (back surface) is 1.5. The layer according to claim 9, which is 10 or more. The layer according to claim 9 or 10, wherein the refractive index n _{D of the} layer is 1.65 or more.   An input / output device comprising the layer according to any one of claims 7 to 11 as a sealing layer.   The process of apply | coating the polymeric composition of any one of Claims 1-6 on a base material and forming a coating film, and the process of bridge-hardening this coating film are included. The method for forming a layer according to any one of the above.   The method for forming a layer according to claim 13, comprising a step of allowing the film to stand for a predetermined time after forming the coating film, and performing the step of crosslinking and curing after the inorganic oxide particles or the siloxane compound is segregated.   The method of forming a layer according to claim 13 or 14, wherein the crosslinking and curing step is performed by irradiating the coating film with ultraviolet rays.