TW201843229A - Metal fluoride dispersed composition, solidification film and laminated glass intermediate layer - Google Patents

Abstract

This metal fluoride dispersed composition contains a polymer of an ethylenically unsaturated bond-containing monomer, a metal fluoride and a dispersion medium. The ethylenically unsaturated bond-containing monomer contains a ring structure-containing (meth)acrylate and an ionic group-containing monomer; and the mass ratio of the ring structure-containing (meth)acrylate to the ionic group-containing monomer, namely (ring structure-containing (meth)acrylate)/(ionic group-containing monomer) is from 0.33 to 3 (inclusive).

Description

   Metal fluoride-dispersed composition, cured film, and laminated glass interlayer   

The present invention relates to a metal fluoride-dispersed composition, a cured film, and an interlayer of laminated glass. In particular, the present invention relates to the curing of a metal fluoride-dispersed composition and a composition containing the metal fluoride-dispersed composition. A cured film of a material and a laminated glass intermediate layer including the cured film.

It is known that low refractive index fine particles are dispersed in a resin composition used as a coating material to further reduce the refractive index of a cured film obtained by coating and curing the resin composition.

As such a low refractive index fine particle, a metal fluoride etc. are known, for example.

Further, as a resin composition containing such low refractive index fine particles, for example, a polyfunctional acrylate containing a carboxyl group-containing (meth) acrylate, a polyfunctional acrylate having three or more acryl fluorenyl groups, and magnesium fluoride has been proposed. A resin composition (for example, refer to the following Patent Document 1).

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 8-244178

In recent years, a lower refractive index than the cured film of the resin composition of Patent Document 1 is required.

The theoretical refractive index of the cured film of the resin composition can be calculated using the Maxwell-Garnett model, but a refractive index lower than the theoretical refractive index is required.

An object of the present invention is to provide a metal fluoride-dispersed composition which can further reduce the refractive index of a cured film and obtain a cured film having a refractive index lower than the theoretical refractive index, so that the metal fluoride is dispersed. A cured film obtained by curing the composition, and a laminated glass intermediate layer including the cured film.

The present invention [1] is a composition dispersed with a metal fluoride, which contains a polymer of a monomer containing an ethylenic unsaturated bond, a metal fluoride, and a dispersion medium, and the monomer containing an ethylenic unsaturated bond includes Mass ratio of the (meth) acrylic acid ester containing a ring structure and the ionic group-containing monomer to the ionic group-containing monomer (the Group) acrylate / ionic group-containing monomer) is 0.33 or more and 3 or less.

The present invention [2] includes the metal fluoride-dispersed composition as described in the above [1], wherein the (meth) ring-containing structure is contained in the ring-containing structure with respect to the total amount of the ethylenically unsaturated bond-containing monomer. The total amount of the acrylate and the ionic group-containing monomer is 65% by mass or more.

The present invention [3] includes the metal fluoride-dispersed composition according to the above [1] or [2], wherein the glass transition temperature of the polymer is 70 ° C or higher and 180 ° C or lower.

The present invention [4] includes the metal fluoride-dispersed composition as described in any one of the above [1] to [3], wherein the average particle diameter of the metal fluoride is 1 nm or more and 10 nm or less.

The present invention [5] includes the metal fluoride-dispersed composition as described in any one of the above [1] to [4], wherein the above-mentioned polymer and the total solid content of the metal fluoride are as described above. The solid content ratio of the polymer is 5 mass% or more and 10 mass% or less.

The present invention [6] includes the metal fluoride-dispersed composition as described in any one of the above [1] to [5], and is a low refractive index coating agent.

The present invention [7] includes a cured film including the cured product of the metal fluoride-dispersed composition as described in any one of the above [1] to [5].

The present invention [8] includes a laminated glass intermediate layer including the low refractive index layer as described in the above [7].

The metal fluoride-dispersed composition of the present invention contains a polymer of an ethylenically unsaturated bond-containing monomer, and the ethylenically unsaturated bond-containing monomer includes a ring-containing (meth) acrylate, and The mass ratio of ionic group-containing monomers (cyclic structure-containing (meth) acrylates to ionic group-containing monomers (cyclic structure-containing (meth) acrylates / ionic group-containing monomers) is 0.33 or more and 3 or less. Therefore, the refractive index of the cured film can be further reduced, and further, it can be further lowered than the theoretical refractive index.

The cured film of the present invention containing the cured product of the metal fluoride-dispersed composition of the present invention has a lower refractive index and a lower refractive index than the theoretical refractive index. Therefore, when the laminated glass intermediate layer includes the cured film, the refractive index of the laminated glass intermediate layer can be further reduced, and the refractive index of the laminated glass intermediate layer can be further reduced.

The laminated glass intermediate layer containing the cured film of the present invention has a lower refractive index and a lower refractive index than the theoretical refractive index. Therefore, the laminated glass intermediate layer has excellent anti-reflection properties.

FIG. 1 shows the blending ratio (Y) of the (meth) acrylic acid ester containing a ring structure and the blending ratio (X) of a monomer containing an ionic group in Examples 1 to 12 and Comparative Examples 1 and 2. ).

The metal fluoride-dispersed composition of the present invention contains a polymer of an ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium. More specifically, the metal fluoride-dispersed composition of the present invention is a polymer in which a monomer containing an ethylenically unsaturated bond and a metal fluoride are dispersed in a dispersion medium. A dispersant for the polymerization of monomers containing ethylenically unsaturated bonds to disperse metal fluoride in a dispersion medium.

The ethylenically unsaturated bond-containing monomer includes a ring structure-containing (meth) acrylate, and an ionic group-containing monomer.

Since the monomer containing an ethylenically unsaturated bond contains a (meth) acrylate having a ring structure, the steric hindrance of the (meth) acrylate due to the ring structure is used to improve the dispersibility of the metal fluoride. In addition, since the ethylenically unsaturated bond-containing monomer includes an ionic group-containing monomer, the affinity of the ionic group-containing monomer and the metal fluoride improves the dispersibility of the metal fluoride. In addition, since the monomer having an ethylenically unsaturated bond includes both a ring-containing (meth) acrylate and an ionic group-containing monomer, the effects of the two are multiplied to make the metal fluoride The dispersion is further improved.

The (meth) acrylate having a ring structure is an acrylate and / or a methacrylate having a ring structure, and examples thereof include a (meth) acrylate having an alicyclic group containing one alicyclic ring, Aliphatic (meth) acrylates of two or more alicyclic rings, (meth) acrylates having an aromatic group, and the like.

Examples of the (meth) acrylate having an alicyclic group containing one alicyclic ring include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, and cyclopentyl (meth) acrylate. , Cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, ethyl cyclohexyl (meth) acrylate, N-butyl cyclohexyl (meth) acrylate, third butyl cyclohexyl (meth) acrylate, dimethyl cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, (methyl ) Tetrahydrofurfuryl acrylate, cyclic trimethylolpropane methylal (meth) acrylate, and the like.

Examples of the (meth) acrylate having an alicyclic group containing two or more alicyclic rings include (meth) acrylic acid Ester, (meth) acrylic acid Ester, (meth) acrylic acid Ester, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate Ester, bicyclo [4.4.0] decyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclopentyl (meth) acrylate, (methyl ) Tricyclopentenyl acrylate, tricyclodecyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, 2-[(2,4-cyclopentadienyl) (meth) acrylate (Oxy) ethyl, (2-methyl-2-ethyl-1,3-dioxolane-4-yl) (meth) acrylate, (3-ethyl (meth) acrylate Oxetane-3-yl) methyl ester and the like.

Examples of the (meth) acrylate having an aromatic group include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxy polyethylene Alcohol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, biphenyl (meth) acrylate, ethoxylated o Phenylphenol (meth) acrylate and the like.

As the (meth) acrylic acid ester having a ring structure, from the viewpoint of improving the effect of steric hindrance between metal fluorides, (A) which has an alicyclic group containing two or more alicyclic rings can be preferably cited. (Meth) acrylic acid ester, (meth) acrylic acid may be better exemplified Ester, (meth) acrylic acid Ester, (meth) acrylic acid (Meth) acrylic acid, adamantyl (meth) acrylate, and (meth) acrylic acid Esters, adamantyl (meth) acrylates, particularly preferably isopropyl acrylate Esters, adamantyl acrylate, and the best examples include methacrylic acid Based ester.

These ring-containing (meth) acrylates can be used alone or in combination of two or more.

Examples of the ionic group-containing monomer include anionic monomers such as a carboxyl group-containing monomer and a phosphate group-containing monomer, such as a tertiary amine group-containing monomer, such as a quaternary ammonium group-containing monomer Cationic monomers, etc.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid (i.e., acrylic acid and / or methacrylic acid), such as itaconic acid, maleic acid, and fumaric acid, and the like. A carboxylic acid or a salt thereof, such as a half-esterified product of a hydroxyalkyl (meth) acrylate and an acid anhydride.

Examples of the phosphoric acid group-containing monomer include (meth) acrylic acid phosphoryloxyethyl esters, mono ((hydroxy) acrylic acid 2-hydroxyethyl ester) phosphoric acid ester-containing (methyl groups) ) Acrylic acid esters, preferably, mono (2-hydroxyethyl (meth) acrylate) phosphate is used.

Examples of the tertiary amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and (meth) acrylic acid. N, N-dimethylaminopropyl, N, N-di-t-butylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, etc. (methyl) N, N-dialkylaminoalkyl acrylates such as N, N-dimethylaminoethyl (meth) acrylamidonium, N, N-diethylaminoethyl (meth) acrylamidonium N, N-dialkylaminoalkyl (meth) acrylamide and the like, N, N-dimethylaminopropyl (meth) acrylamide, and the like, preferably (meth) acrylic acid N N, N-dialkylamino alkyl ester, more preferably N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino methacrylate Ethyl ester.

The quaternary ammonium group-containing monomer is, for example, a quaternizing agent (e.g., epihalohydrin, benzyl halide, alkyl halide, etc.) acting on the tertiary amine group-containing monomer, specifically, In other words, for example, 2- (methpropenyloxy) ethyltrimethylammonium chloride, 2- (methpropenyloxy) ethyltrimethylammonium bromide, and 2- (methacrylic acid) (Meth) acryloxyalkyltrialkylammonium salts such as (oxy) ethyltrimethylammonium dimethylphosphate, such as methacrylamidoaminopropyltrimethylammonium chloride, methacryl (Meth) acrylamidoalkyl trialkylammonium salts such as amidopropyltrimethylammonium bromide, for example, tetraalkyl (meth) acrylates such as tetrabutylammonium (meth) acrylate, For example, trialkylbenzyl ammonium (meth) acrylate such as trimethylbenzyl ammonium (meth) acrylate and the like.

As an ionic group-containing monomer, from the viewpoint of achieving an affinity improvement on the surface of a metal fluoride having a hydrophilic property, an anionic monomer may be preferably listed, and a carboxyl group-containing monomer may be more preferably listed. More preferably, (meth) acrylic acid may be mentioned, and further, methacrylic acid may be mentioned.

These ionic group-containing monomers can be used alone or in combination of two or more.

The ethylenically unsaturated bond-containing monomer preferably contains a copolymerizable monomer.

Copolymerizable monomers (except for ring structure-containing (meth) acrylates and monomers containing ionic groups) are copolymerizable monomers with ring structure-containing (meth) acrylates and monomers containing ionic groups Examples of the monomer include: (meth) acrylic acid alkyl esters, styrenes, reactive functional group-containing monomers, maleic acid esters such as dimethyl maleate, and fumaric acid Fumarate such as dimethyl ester, acrylonitrile, methacrylonitrile, vinyl acetate, and the like. The (meth) acrylic acid alkyl ester includes alkyl acrylate and / or alkyl methacrylate.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl) Base) n-butyl acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, new (meth) acrylate Amyl ester, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, thirteen (meth) acrylate Alkyl ester, tetradecyl (meth) acrylate, 1-methyltridecyl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate Esters (stearyl (meth) acrylate), isostearyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate ((meth) acrylic acid Dodecyl Ester), (meth) acrylic acid Alkyl esters, tridecyl (meth) acrylates, and the like, linear or branched (meth) acrylic acid alkyls having 1 to 30 carbons, preferably straight-chains having 1 to 30 carbons As the alkyl (meth) acrylate, linear alkyl (meth) acrylate having 2 to 4 carbon atoms can be more preferably exemplified, and n-butyl (meth) acrylate and (formaldehyde) can be more preferably exemplified. Based) isobutyl acrylate.

As the styrenes, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, etc. may be preferred. List styrene.

Examples of the reactive functional group-containing monomer include: an isocyanate-containing monomer, a hydroxyl-containing monomer, and a glycidyl-containing monomer.

The isocyanate-containing monomer has an isocyanate group as a reactive functional group, and examples thereof include: (meth) acrylic acid isocyanatomethyl ester, (meth) acrylic acid 2-isocyanatoethyl ester, ( 3-isocyanatopropyl meth) acrylate, 1-methyl-2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, (meth) 4-isocyanatobutyl acrylate and the like.

The hydroxyl-containing monomer has a hydroxyl group as a reactive functional group, and examples thereof include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (formaldehyde) 1-methyl-2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc., preferably 2-hydroxy (meth) acrylate Ethyl ester and 3-hydroxypropyl (meth) acrylate are more preferably exemplified by 2-hydroxyethyl acrylate and 3-hydroxypropyl methacrylate.

The glycidyl group-containing monomer has glycidyl group as a reactive functional group, and examples thereof include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether. And other glycidyl-containing monomers.

As the copolymerizable monomer, from the viewpoint of adjusting the glass transition temperature of a polymer of an ethylenically unsaturated bond-containing monomer (to be described later), a styrene-based monomer or a reactive functional group-containing monomer can be preferably cited. More preferably, a hydroxy-containing monomer, styrene, and more preferably, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and styrene can be further preferably used.

These copolymerizable monomers can be used alone or in combination of two or more.

The reactive functional group derived from the reactive functional group-containing monomer can be reacted with an active energy ray-curable monomer (described later).

The blending ratio of the (meth) acrylic acid ester containing a ring structure is relative to the total amount of monomers containing an ethylenically unsaturated bond (i.e., the (meth) acrylic acid ester containing a ring structure, the monomer containing an ionic group And the total amount of copolymerizable monomers), for example, 16.25% by mass or more, preferably 25% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more It is, for example, 75% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.

If the blending ratio of the ring-containing (meth) acrylate is within the above range, the refractive index of the cured film (described later) obtained by using a composition in which metal fluoride is dispersed can be further reduced, and it can be refracted more theoretically. The rate (described later) is further reduced.

The blending ratio of the ionic group-containing monomer is 16.25 mass% or more, preferably 25 mass% or more, and more preferably 30 mass% or more, relative to the total amount of the ethylenically unsaturated bond-containing monomer. It is more preferably 35 mass% or more, and for example, 75 mass% or less, more preferably 65 mass% or less, more preferably 55 mass% or less, and still more preferably 45 mass% or less.

If the blending ratio of the ionic group-containing monomer is within the above range, the refractive index of the cured film (described later) obtained by using a composition in which metal fluoride is dispersed can be further reduced, and it can be lower than the theoretical refractive index (described later) )Further decrease.

Specifically, if the blending ratio of the ionic group-containing monomer is 22% by mass or more and less than 29% by mass, the blending ratio of the (meth) acrylate containing a ring structure is, for example, 60% by mass or more and 70% by mass. %the following.

In addition, if the blending ratio of the ionic group-containing monomer is 29% by mass or more and less than 55% by mass, the blending ratio of the ring structure-containing (meth) acrylate is, for example, 35% by mass or more, preferably 40 At least mass%, for example, less than 60% by mass, preferably less than 55% by mass.

In addition, if the blending ratio of the ionic group-containing monomer is 55% by mass or more and 70% by mass or less, the blending ratio of the (meth) acrylate containing a ring structure is, for example, 20% by mass or more and less than 35% by mass .

That is, when the blending ratio of the monomer containing an ionic group is small, by increasing the blending ratio of the (meth) acrylate containing a ring structure, the blending ratio of the monomer containing an ionic group is smaller. In many cases, the refractive index of a cured film (described later) obtained by using a composition in which a metal fluoride is dispersed can be further reduced by reducing the blending ratio of the (meth) acrylate containing a ring structure. It is further lower than the theoretical refractive index (described later).

The mass ratio of the (meth) acrylate containing a ring structure to the monomer containing an ionic group (the (meth) acrylate containing a ring structure / the monomer containing an ionic group) is 0.33 or more, preferably 0.50 The above is more preferably 0.80 or more, further preferably 1.0 or more, and, for example, 3.0 or less, more preferably 2.3 or less, and even more preferably 1.5 or less.

If the above-mentioned mass ratio is above the above-mentioned lower limit or below the above-mentioned upper limit, the refractive index of the cured film (to be described later) obtained by using a composition in which metal fluoride is dispersed can be further reduced, and it can be further lowered than the theoretical refractive index (to be described later) .

On the other hand, if the above-mentioned mass ratio is less than the above-mentioned lower limit or exceeds the above-mentioned upper limit, the refractive index of the cured film (described later) obtained by using a composition in which metal fluoride is dispersed is in a case where it is above the above-mentioned lower limit or below the above-mentioned upper limit The ratio becomes higher.

The total amount of the cyclic structure-containing (meth) acrylate and the ionic group-containing monomer is, for example, 60% by mass or more, and preferably 65% by mass or more, with respect to the total amount of the monomer having an ethylenically unsaturated bond. 67% by mass or more, more preferably 70% by mass or more, more preferably 75% by mass or more, and further 77% by mass or more, and the upper limit is not particularly limited, and is, for example, 100% by mass or less, preferably 99.9% by mass % Or less, preferably 95% by mass or less.

If the total amount of the ring-containing (meth) acrylate and the ionic group-containing monomer is at least the above-mentioned lower limit, the refractive index of the cured film (described later) obtained by using a composition in which a metal fluoride is dispersed can be further reduced. The refractive index can be lowered further than the theoretical refractive index (described later).

The blending ratio (Y) of the ring-containing (meth) acrylate and the blending ratio (X) of the ionic group-containing monomer are preferably those satisfying the following formulae (1) to (4). relationship.

Y ≧ 0.33X (1)

Y ≦ 3X (2)

X + Y ≧ 65 (3)

X + Y ≦ 100 (4)

Specifically, the above-mentioned formulas (1) to (4) are obtained by examples described later.

If the blending ratio of the (meth) acrylate containing a ring structure and the blending ratio of the monomer containing an ionic group satisfies the above formula (1) to the above formula (4), the use of metal fluoride dispersed can be further reduced. The refractive index of the cured film (to be described later) obtained by the composition can be lowered further than the theoretical refractive index (to be described later).

Copolymerizable mono-system (meth) acrylate with ring structure and the remainder of the ionic group-containing monomer, specifically, the copolymerizability with respect to the total amount of the ethylenically unsaturated bond-containing monomer The blending ratio of the monomer is, for example, 0.1 mass% or more, preferably 5 mass% or more, and, for example, 40 mass% or less, preferably 35 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass % Or less, and further 20% by mass or less.

If the blending ratio of the copolymerizable monomer is equal to or less than the above upper limit, the refractive index of the cured film (described later) obtained by using a composition in which metal fluoride is dispersed can be further reduced, and it can be further improved than the theoretical refractive index (described later). reduce.

The polymer of such an ethylenically unsaturated bond-containing monomer is not particularly limited. For example, the aforementioned monomer component (a ring-containing structure (A) may be obtained by a known polymerization method such as block polymerization, solution polymerization, or suspension polymerization. Group) an acrylate, an ionic group-containing monomer, and a copolymerizable monomer) obtained by radical polymerization. A polymer of an ethylenically unsaturated bond-containing monomer is preferably obtained by solution polymerization.

In the solution polymerization, a polymerization initiator and the like are prepared in a solvent together with the monomer component to perform polymerization.

The polymerization initiator is not particularly limited, and may be appropriately selected depending on the purpose and application, and examples thereof include known radical polymerization initiators.

Examples of the radical polymerization initiator include azo compounds, peroxide compounds, thioethers, sulfins, sulfinates, diazo compounds, and redox compounds. Preferably, an azo compound is mentioned.

Examples of the azo-based compound include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanonitrile, 1,1'-azobis (1-acetamidooxy-1- Phenylethane), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methyl Butyronitrile), and the like, preferably 2,2'-azobis (2-methylbutyronitrile).

The blending ratio of the polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, and, for example, 13 parts by mass or less with respect to 100 parts by mass of the total amount of the ethylenically unsaturated bond-containing monomer. It is preferably 10 parts by mass or less.

These polymerization initiators can be used alone or in combination of two or more.

The solvent is not particularly limited as long as it is stable with respect to the above monomer components, and examples thereof include organic solvents and aqueous solvents.

Examples of the organic solvent include petroleum-based hydrocarbon solvents such as hexane and mineral spirits, and aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and dioxane. Ketone solvents such as isobutyl ketone and cyclohexanone, such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and other ester solvents, such as N, N-di Aprotic polar solvents such as methylformamide, N, N-dimethylacetamide, dimethylsulfinium, N-methylpyrrolidone, and pyridine.

Examples of the water-based solvent include water, for example, alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and butanol, and glycol-ether solvents such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

The solvent can also be obtained in the form of a commercially available product. Specifically, as the petroleum-based hydrocarbon solvent, for example, AF solvent No. 4 to 7 (the above are manufactured by Nippon Oil Corporation), etc., as the aromatic hydrocarbon-based solvent, For example, ink solvent No. 0, Solvesso 100, 150, and 200 manufactured by Exxon Chemical Company (the above are manufactured by Nippon Oil Corporation) and the like.

The blending ratio of the solvent is not particularly limited, and can be appropriately set according to the purpose and application.

These solvents can be used alone or in combination of two or more.

The polymerization conditions in the solution polymerization differ depending on the types of the monomer component, the polymerization initiator, and the solvent described above. The polymerization temperature is, for example, 30 ° C or higher, preferably 60 ° C or higher, and, for example, 150 ° C or lower. The temperature is 120 ° C. or lower, and the polymerization time is, for example, 2 hours or longer, preferably 4 hours or longer, and, for example, 20 hours or shorter, and preferably 8 hours or shorter.

Thereby, a polymer of an ethylenically unsaturated bond-containing monomer can be obtained.

Furthermore, when the composition containing a metal fluoride-dispersed polymer containing a polymer containing an ethylenically unsaturated bond-containing monomer is cured (hardened) by light irradiation, the ethylenically unsaturated bond-containing monomer is polymerized. A reactive functional group derived from the above-mentioned reactive functional group-containing monomer in the polymer and / or an ionic group derived from the aforementioned ionic group-containing monomer, and having a reactive functional group capable of interacting with these reactive functional groups and / Or the reactive energy functional group-containing monomer having an active energy ray-curable group reacts with the ionic group, and the polymer of the ethylenically unsaturated bond-containing monomer is modified.

The active energy ray-curable group-containing monomer has a reaction capable of reacting with the reactive functional group derived from the reactive functional group-containing monomer and / or the ionic group derived from the aforementioned reactive functional group-containing monomer. Functional group and active energy ray-curable group.

The active energy ray-curable group is a functional group containing an ethylenic double bond that exhibits curability by irradiation with active energy rays. Specifically, for example, a (meth) acrylfluorenyl group may be mentioned. The (meth) acrylfluorenyl group includes acrylfluorenyl and methacrylfluorenyl.

Examples of the active energy ray-curable monomer include an isocyanate-containing monomer having, as a reactive functional group, an isocyanate group that is a functional group that can be bonded to a hydroxyl group. A carboxyl group-containing monomer having a glycidyl-bonded functional group as a reactive functional group, for example, a hydroxyl-containing monomer having a hydroxyl group belonging to a functional group capable of bonding to an isocyanate group as a reactive functional group, For example, a glycidyl group-containing monomer having a glycidyl group which is a functional group capable of bonding to a carboxyl group and a phosphate group as a reactive functional group, for example, a phosphate group having a functional group which can be bonded to a glycidyl group as a reaction Phosphate group-containing monomers, etc.

Examples of the isocyanate group-containing monomer, the hydroxyl group-containing monomer, and the glycidyl group-containing monomer are the same as those exemplified for the above-mentioned copolymerizable monomer.

Examples of the carboxyl group-containing monomer and the phosphate group-containing monomer are the same as those exemplified for the ionic group-containing monomer.

The blending ratio of the monomer containing an active energy ray-curable group is, for example, 1% by mass or more, preferably 3% by mass or more, for example, 66% by mass relative to the total amount of the monomers containing ethylenically unsaturated bonds. Hereinafter, it is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 20% by mass or less, and even more preferably 15% by mass or less.

When the ionic group derived from the ionic group-containing monomer is reacted with the reactive functional group derived from the active energy ray-curable monomer, the ionic group The ionic group of the monomer of the radical reacts with the reactive functional group derived from the monomer containing the active energy ray-curable group, while adjusting the monomer containing the ionic group and the ring-containing structure (a Based on the mass ratio of acrylate).

Specifically, the above-mentioned mass ratio of the (meth) acrylate having a ring structure to the monomer containing an ionic group (the monomer containing an ionic group that does not contribute to the reaction) ) Acrylate / ionic group-containing monomer (ionic group-containing monomer which does not contribute to the reaction)) is prepared in such a manner as to fall within the above range.

When a reactive functional group derived from a monomer containing an active energy ray-curable group is an ionic group, it is prepared such that the above-mentioned mass ratio falls within the above range in the same manner as described above.

Thereby, the polymer of the monomer containing an ethylenically unsaturated bond is modified. Specifically, an active energy ray-curable group is introduced into a side chain of a polymer of an ethylenically unsaturated bond-containing monomer. Therefore, a composition containing such a polymer of an ethylenically unsaturated bond-containing monomer dispersed with a metal fluoride can be cured (hardened) by light irradiation.

The glass transition temperature of the polymer of the ethylenically unsaturated bond-containing monomer is, for example, 55 ° C or higher, preferably 70 ° C or higher, more preferably 85 ° C or higher, and further preferably 100 ° C or higher, such as 200 ° C or lower, The temperature is preferably 180 ° C or lower, and more preferably 160 ° C or lower.

If the glass transition temperature of the polymer of an ethylenically unsaturated bond-containing monomer is at least the above lower limit, the refractive index of a cured film (described later) obtained by using a composition in which a metal fluoride is dispersed can be further reduced. It is further lower than the theoretical refractive index (described later).

If the glass transition temperature of the polymer of an ethylenically unsaturated bond-containing monomer is equal to or lower than the above-mentioned upper limit, the cured film obtained by using a composition in which a metal fluoride is dispersed is excellent in flexibility.

The polymer glass transition temperature of the ethylenically unsaturated bond-containing monomer is calculated by the FOX formula.

The weight average molecular weight of polyethylene-styrene conversion of a polymer of an ethylenically unsaturated bond-containing monomer obtained by gel permeation chromatography is, for example, 500 or more, preferably 3,000 or more, and, for example, 20,000 or less Is preferably 10,000 or less.

The metal fluoride is dispersed in the metal fluoride dispersed composition in order to reduce the refractive index of a cured film obtained by using the metal fluoride dispersed composition.

Examples of the metal fluoride include alkali metal fluoride, alkaline earth metal fluoride, aluminum fluoride, cryolite (3NaF‧AlF ₃ , Na ₃ AlF ₆ ), and the like.

Examples of the alkali metal fluoride include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride.

Examples of the alkaline earth metal fluoride include magnesium fluoride, calcium fluoride, strontium fluoride, and barium fluoride.

Preferred examples of the metal fluoride include alkaline earth metal fluorides, and more preferred is magnesium fluoride.

These metal fluorides can be used alone or in combination of two or more.

The average particle diameter of the metal fluoride is, for example, 1 nm or more, preferably 3 nm or more, more preferably 6 nm or more, and, for example, 100 nm or less, preferably 30 nm or less, more preferably 15 nm or less, and further preferably 12 nm or less, It is particularly preferably at most 10 nm.

When the average particle diameter of the metal fluoride is at least the above lower limit, the dispersibility of the metal fluoride can be improved.

If the average particle diameter of the metal fluoride is below the above upper limit, the refractive index of the cured film (to be described later) obtained by using the composition in which the metal fluoride is dispersed can be further reduced, and it can be further lowered than the theoretical refractive index (to be described later). . In addition, smoothness can be improved.

The method for measuring the average particle diameter will be described in detail in Examples described later.

The solid content ratio of the polymer of the ethylenically unsaturated bond-containing monomer polymer and the total solid content of the metal fluoride is 5.0% by mass or more, and preferably 7.0 The mass% or more is, for example, 30 mass% or less, preferably 15 mass% or less, more preferably 12 mass% or less, and even more preferably 10 mass% or less.

When the solid content ratio is greater than or equal to the above lower limit, the dispersibility of the metal fluoride can be improved.

When the solid content ratio is equal to or less than the upper limit described above, the refractive index of a cured film (to be described later) obtained by using a composition in which a metal fluoride is dispersed can be further lowered, and the theoretical refractive index (to be described later) can be further reduced.

The solid content ratio of the metal fluoride relative to the total solid content of the polymer of the ethylenically unsaturated bond-containing monomer and the metal fluoride is 70% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass % Or more and, for example, 95% by mass or less, and preferably 93% by mass or less.

The dispersion medium is a liquid in which the metal fluoride is dispersed, and examples thereof include the above-mentioned solvents used in the case of polymerizing a polymer containing a monomer having an ethylenically unsaturated bond by solution polymerization.

From the viewpoint of achieving improvement in work efficiency, it is preferable to use a solvent used at this time as a dispersion medium when the polymer of a monomer containing an ethylenically unsaturated bond is subjected to solution polymerization.

As the dispersion medium, an aqueous solvent is preferably used, and a glycol ether solvent is further preferably used.

The blending ratio of the dispersion medium is, for example, 1 mass% or more, preferably 3 mass% or more, and, for example, 99 mass% or less, and preferably 95 mass% or less with respect to the composition in which the metal fluoride is dispersed.

Such a metal fluoride-dispersed composition is not particularly limited. For example, it can be obtained by blending a polymer of the above ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium. The polymer of the monomer containing an ethylenically unsaturated bond and the metal fluoride are dispersed in a dispersion medium.

The method for dispersing the polymer of the ethylenically unsaturated bond-containing monomer and the metal fluoride is not particularly limited, and examples thereof include the use of a paint shaker, a roll mill, a ball mill, a mill, a sand mill, A method of dispersing by a known dispersing machine such as a bead mill and an ultrasonic dispersing machine. From the viewpoint of achieving improvement in coatability, coating stability, and transparency of a cured film (described later), a ball mill, A bead mill can be better exemplified.

When a bead mill is used as the disperser, a known dispersion medium such as zirconia beads and glass beads can be used.

The diameter of the beads in the dispersion medium is not particularly limited, and is, for example, 10 μm or more, and, for example, 500 μm or less, and preferably 100 μm or less. The filling rate of the dispersion medium can be appropriately set depending on the purpose and application.

When a bead mill or a ball mill is used as a disperser, the above-mentioned dispersion medium may be used to pulverize the metal fluoride to adjust the average particle diameter to the above range. In this case, a metal fluoride having an average particle diameter larger than the above range can be prepared in a disperser.

The dispersion time is, for example, 10 hours or more, preferably 20 hours or less, and, for example, 36 hours or less.

The composition in which the metal fluoride is dispersed may include a polymerizable compound (hardener) such as a polyfunctional acrylate or a polyfunctional isocyanate, a known additive, and the like. When the composition in which the metal fluoride is dispersed contains a polymerizable compound, the composition in which the metal fluoride is dispersed is hardened by light irradiation or heating.

Thereby, a polymer containing a monomer containing an ethylenically unsaturated bond, a metal fluoride, and a dispersion medium-dispersed composition can be obtained.

In such a metal fluoride-dispersed composition, a dispersion medium is used to disperse the polymer of the ethylenic unsaturated bond-containing monomer and the metal fluoride.

The composition in which the metal fluoride is dispersed can be used as various coating agents (preferably low refractive index coating agents).

The low refractive index coating agent is a coating agent that can obtain a cured film (described later) having a low refractive index, and can be used for various optical-related members requiring a low refractive index.

The low refractive index of the low refractive index coating agent means that the refractive index of a cured film (to be described later) obtained by using the low refractive index coating agent is less than 1.35, preferably 1.312 or less, and more preferably 1.297 or less. It is preferably 1.285 or less, particularly preferably 1.283 or less, and further 1.28 or less.

Further, a cured film can be obtained by applying a composition (coating agent) in which a metal fluoride is dispersed to a substrate and drying the dispersion medium.

Furthermore, when an active energy ray-hardening group is introduced into the side chain of a polymer of an ethylenically unsaturated bond-containing monomer, or when a metal fluoride-dispersed composition includes the above-mentioned polymerizable compound, A cured film (cured film) can be obtained by applying a composition in which a metal fluoride is dispersed to a substrate, drying the dispersion medium, and then performing light irradiation or heat curing.

That is, the cured film of this invention contains the hardened | cured material of the composition which disperse | distributed the metal fluoride mentioned above.

The substrate is not particularly limited, and examples thereof include polycarbonate, polymethyl methacrylate, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin, epoxy resin, and melamine. Resin, triacetam cellulose resin, acrylonitrile-butadiene-styrene (ABS, Acrylonitrile Butadiene Styrene) resin, acrylonitrile-styrene (AS, Acrylonitrile Styrene) resin, Plastic such as olefin resin, or metal, wood, paper, glass, slate, etc.

The coating method is not particularly limited, and for example, a roll coater, a spin coater, a bar coater, a doctor blade, a Meyer bar coater, or an air knife can be used. Coating, or well-known coating methods such as screen printing, offset printing, quick-drying printing, brush coating, spray coating, gravure coating, and reverse gravure coating.

As drying conditions, the drying temperature is, for example, 20 ° C or higher, preferably 60 ° C or higher, for example, 200 ° C or lower, preferably 150 ° C or lower, and the drying time is, for example, 0.5 minute or longer, preferably 1 minute or longer, and, for example, It is 30 minutes or less, preferably 5 minutes or less.

The film thickness after drying is, for example, 50 nm or more, preferably 500 nm or more, and, for example, 10 μm or less, and preferably 7 μm or less.

Thereby, a cured film including the cured product of the metal fluoride-dispersed composition can be obtained.

In addition, such a cured film has a lower refractive index due to a cured product containing the metal fluoride-dispersed composition.

Specifically, the refractive index of the cured film is, for example, less than 1.35, preferably 1.312 or less, more preferably 1.297 or less, even more preferably 1.285 or less, even more preferably 1.283 or less, and even 1.282 or less.

On the other hand, the refractive index of the cured product of the resin composition can be calculated using the Maxwell-Garnett model.

The cured film has a refractive index lower than the theoretical refractive index calculated using the Maxwell-Garnett model because of the cured product containing the metal fluoride dispersed composition.

Specifically, the refractive index difference is, for example, 0.051 or more, preferably 0.086 or more, more preferably 0.101 or more, still more preferably 0.116 or more, 0.12 or more, particularly preferably 0.131 or more, and, for example, 2 or less.

The Maxwell-Garnett model is a model that calculates the relative dielectric constant of a fine particle-dispersed resin obtained by dispersing a nano-sized content in a matrix resin, and is expressed by the following formula (5).

In the above formula (5), ε _av represents the relative dielectric constant of the fine particle-dispersed resin, ε _p represents the relative dielectric constant of the nano-sized content, and ε _m represents the relative dielectric constant of the matrix resin.

The relative permittivity is calculated by the following formula (6).

Relative permittivity = refractive index ² × relative permeability (6)

Since the relative magnetic permeability of a non-magnetic substance is 1.0, the above formula (6) can be rewritten as the following formula (7).

Relative permittivity = refractive index ² (7)

Based on the above formula (7), the above formula (5) can be rewritten as the following formula (8).

In the above formula (8), n _av represents the refractive index of the fine particle dispersion resin, and specifically, the theoretical refractive index of a cured film containing a cured product of a composition in which a metal fluoride is dispersed.

In the above formula (8), n _p represents a refractive index of a nano-sized content, and specifically, a refractive index of a metal fluoride.

In the above formula (8), n _m represents the refractive index of the matrix resin, and specifically, the refractive index of a polymer of a monomer containing an ethylenically unsaturated bond.

η can be represented by the following formula (9).

η = volume of nano-sized inclusions / (volume of matrix resin + volume of nano-sized inclusions) (9)

In addition, the volume of the nano-sized contents and the volume of the matrix resin can be calculated by the following formula (10) and the following formula (11), respectively.

Volume of nano-sized inclusions = mix ratio of nano-sized inclusions / specific gravity of nano-sized inclusions (10)

Volume of matrix resin = formulation ratio of matrix resin / specific gravity of matrix resin (11)

In this way, a cured film having a refractive index lower than the theoretical refractive index can be obtained.

Such a cured film is useful for various optical-related members requiring a low refractive index, and among them, it is very useful as a laminated glass intermediate layer.

The laminated glass intermediate layer of the present invention includes the above-mentioned cured film.

The laminated glass intermediate layer is a layer (resin layer) sandwiched between a pair of glass plates.

The laminated glass intermediate layer includes the above-mentioned cured film, and therefore has a lower refractive index and a lower refractive index than a theoretical refractive index. Therefore, the laminated glass intermediate layer has excellent anti-reflection properties.

The laminated glass intermediate layer can be used for producing laminated glass.

Laminated glass is obtained, for example, by sandwiching a laminated glass intermediate layer between a pair of glass plates, and thereafter laminating a pair of glass plates with the laminated glass using an autoclave and a press. .

Furthermore, a resin layer other than the laminated glass intermediate layer may be sandwiched between a pair of glass plates.

In this case, the laminated glass intermediate layer may be sandwiched between the glass plate and other resin layers, and may also be sandwiched between other resin layers and other resin layers.

Examples of the other resin layer include a resin layer containing a butyraldehyde resin.

Since such a laminated glass includes an intermediate layer of laminated glass, it has excellent anti-reflection properties.

In addition, such laminated glass is used in various applications, for example, as a windshield, a side window, a rear windshield of an automobile, or a window glass of an aircraft or a building.

    [Example]    

Specific numerical values such as the blending ratio (containing ratio), physical property values, and parameters used in the following description may be replaced by corresponding blending ratios (containing ratio), physical property values, and parameters, etc., described in the above-mentioned "Embodiment". Record the upper limit value (defined as a value "below" and "less than") or the lower limit value (defined as a value "above" and "exceeds"). In addition, unless specifically mentioned in the following description, "part" and "%" are quality standards.

    1. Manufacture of polymer of monomer containing ethylenic unsaturated bond         (Synthesis example 1)    

In a flask equipped with a stirrer, a condenser, a thermometer, an inert gas introduction tube, and a dropping funnel, 100 parts of propylene glycol monomethyl ether (PGME) was added, and an inert gas (nitrogen) was introduced, and the temperature was raised to 110 ° C. Thereafter, using a dropping funnel, the methacrylic acid isocyanate containing (meth) acrylate as a ring-containing structure was added dropwise over 2 hours with stirring. 50 parts of base esters, 40 parts of methacrylic acid as an ionic group-containing monomer, 9.7 parts of styrene as a copolymerizable monomer, 0.1 parts of isobutyl methacrylate, 0.1 parts of 2-hydroxyethyl acrylate, A mixture of 0.1 parts of 3-hydroxypropyl methacrylate and 8 parts of 2,2'-azobis (2-methylbutyronitrile) as a polymerization initiator. After 1 time, 2 parts of 2,2'-azobis (2-methylbutyronitrile) as a polymerization initiator was added, and a reaction was performed for 3 hours. Thereby, a polymer of an ethylenically unsaturated bond-containing monomer is obtained.

    (Synthesis example 2 to synthesis example 16)    

Except having changed the formulation according to the description of Table 1, it processed similarly to the synthesis example 1, and obtained the polymer of the ethylenic unsaturated bond containing monomer.

    2. Manufacturing of metal fluoride dispersed composition and cured film         (Example 1)    

91 parts of a polymer of an ethylenically unsaturated bond-containing monomer obtained in Synthesis Example 1 in terms of solid content conversion, magnesium fluoride (manufactured by Central Glass, magnesium fluoride No. 4 (MgF ₂ )) 809 parts of PGME as a solvent and 1500 parts of 50 μm zirconia beads as a dispersing medium were added to a 300 mL bottle, and a disperser (manufactured by Seiwa Giken, Rocking Shaker RS-05W) was used to dissolve magnesium fluoride at 60 Hz for 24 hours. Crush and disperse. Thereafter, the zirconia beads were removed by filtration, thereby obtaining a metal fluoride-dispersed composition in which magnesium fluoride was dispersed. The solid content of the obtained metal fluoride dispersed composition was 11% by mass.

Then, the composition in which the metal fluoride was dispersed was formed on a glass plate (manufactured by Taiyou Machinery Co., Ltd., 2 mm) with a spin coater, and measured using a reflection spectrometer Fe-3000 (manufactured by Otsuka Electronics Co., Ltd.). The film thickness was formed so that the film thickness became 0.5 μm. Then, it dried at 80 degreeC for 1 minute, and hardened | cured, and the cured film was obtained.

    (Examples 2 to 16 and Comparative Examples 1 to 4)    

Except that the formulation and dispersion time were changed as described in Table 2, the same treatment as in Example 1 was performed to obtain a metal fluoride-dispersed composition and a cured film.

Furthermore, in Comparative Example 3, silica particles (Avosil, manufactured by Evonik, Aerosil R812) were used instead of magnesium fluoride, and the modification was performed as described in Table 2. Except that, the same treatment as in Example 1 was performed to obtain dispersion. It has a composition of silicon dioxide and a cured film.

Furthermore, in Comparative Example 4, ARONIX M5300 (carboxy polycaprolactone monoacrylate, manufactured by Toa Kosei Co., Ltd.) was used in place of a polymer of an ethylenically unsaturated bond-containing monomer.

    3. Evaluation         1) average particle size    

For each of the compositions containing metal fluoride dispersed in Examples 1 to 16 and Comparative Examples 1 to 4, Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) was used with a laser light diffraction / scattering particle size distribution measuring device. The measurement was performed under the following conditions. The results are shown in Table 2.

Measurement times: 1 time

Measurement time: 180 seconds

Measurement temperature: 23 ° C

Average particle size: cumulative 50% of the volume average particle size

Measurement solvent: the dispersion medium used in the preparation of the dispersion

CI value: 0.4 ~ 0.8

Particle permeability: through

Sensitivity: Standard

Filter: Stand: Norm

Nano range correction: invalid

    2) Weight average molecular weight obtained by gel permeation chromatography    

Each of the polymers of the ethylenically unsaturated bond-containing monomers in Synthesis Example 1 to Synthesis Example 16 was dissolved in tetrahydrofuran so that the sample concentration became 1.0 g / L, and a differential refractive index detector (RID) was used. The gel permeation chromatography (GPC) was performed to obtain the molecular weight distribution of the sample.

Then, based on the obtained chromatogram (graph), a standard polystyrene was used as a calibration curve to calculate the weight average molecular weight (Mw) of the sample. The measurement apparatus and measurement conditions are shown below. The results are shown in Table 1.

Data processing device: Product number HLC-8220GPC (manufactured by Tosoh)

Differential refractive index detector: RI (Refractive Index) detector built into the product number HLC-8220GPC

Column: 2 TSKgel SuperHZM-H (manufactured by Tosoh)

Mobile phase: tetrahydrofuran

Column flow: 0.35mL / min

Sample concentration: 1.0g / L

Injection volume: 10 μL

Measurement temperature: 40 ° C

Molecular weight marker: Standard polystyrene (standard material manufactured by POLYMER LABORATORIES LTD.) (Using POLYSTYRENE-MEDIUM MOLECULAR WEIGHT CALIBRATION KIT)

    3) refractive index    

The refractive index (measured refractive index) of each cured film of Examples 1 to 16 and Comparative Examples 1 to 4 was measured using a reflection spectrofilm thickness meter Fe-3000 (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 2.

In addition, the theoretical refractive indices of the cured films of Examples 1 to 16 and Comparative Examples 1 to 4 were calculated using the Maxwell-Garnett model.

Specifically, the refractive index (n _av ) (theoretical refractive index) of the cured film of the composition in which the metal fluoride is dispersed is calculated using the above formulas (8) to (11).

In Example 1, the refractive index (n _m ) of a polymer of an ethylenically unsaturated bond-containing monomer was set to 1.53, the refractive index (n _p ) of a metal fluoride was set to 1.38, The proportion of the polymer of the saturated bond monomer is set to 0.09, the proportion of the metal fluoride compound is set to 0.91, the proportion of the polymer of the monomer containing an ethylenically unsaturated bond is 1.1, and the proportion of the metal fluoride compound is 1.1. The specific gravity was set to 3.14, and the theoretical refractive index was calculated. The results are shown in Table 2.

Furthermore, the specific gravity of the polymer containing an ethylenically unsaturated bond-containing monomer and the specific gravity of ARONIX M5300 are based on the use of a vibration density-specific gravity meter DMA 4500M (manufactured by Anton Paar JAPAN). % -10%) A linear approximation of the specific gravity value of each, and the estimated specific gravity (NV) = 100% of the polymer of the monomer containing an ethylenically unsaturated bond. The measurement conditions are shown below.

Measurement times: once for each concentration condition

Concentration (NV): 50%, 30%, 10%

Diluted solvent: PGME

Measurement temperature: 23 ° C

The specific gravity of the metal fluoride is 3.15, which is a known specific gravity value of the metal fluoride.

For each of the cured films of Examples 2 to 16 and Comparative Examples 1 to 4, the theoretical refractive index was calculated in the same manner as in Example 1.

Then, the difference between the obtained theoretical refractive index and the obtained measured refractive index (theoretical refractive index-measured refractive index) (refractive index difference) is calculated. The results are shown in Table 2.

    4) Dispersion    

The centrifugal separator H-1500F manufactured by KOKUSAN Co., Ltd. was used to centrifuge each of the compositions in which metal fluoride was dispersed in Examples 1 to 16 and Comparative Examples 1 to 4, and magnesium fluoride was visually confirmed. Decentralized. The results are shown in Table 2. The evaluation of dispersibility is as follows.

A +: When centrifugation was performed at 10,000 rpm for 1 hour, the precipitate could not be confirmed.

A: When the centrifugation was performed at 5000 rpm for 1 hour, no precipitate was confirmed. When the centrifugation was performed at 10,000 rpm for 1 hour, the precipitate was confirmed.

B: When the centrifugal separation was performed at 2000 rpm for 1 hour, no precipitate was confirmed. When the centrifugal separation was performed at 5000 rpm for 1 hour, the precipitate was confirmed.

C: When the centrifugation was performed at 500 rpm for 1 hour, no precipitate was confirmed. When the centrifugation was performed at 2000 rpm for 1 hour, the precipitate was confirmed.

D: A precipitate was confirmed before centrifugation.

    4. Explore    

1) The mass ratio of the (meth) acrylate with a ring structure to the monomer containing an ionic group (the (meth) acrylate with a ring structure / the monomer with an ionic group) is 0.33 or more and 3 or less Examples 1 to 16 showed a lower refractive index and a higher refractive index difference than the comparative example 1 having a mass ratio of 3.29 and the comparative example 2 having a mass ratio of 0.27.

From this, it can be seen that if the mass ratio of the (meth) acrylate containing a ring structure to the monomer containing an ionic group (the (meth) acrylate containing a ring structure / the monomer containing an ionic group) is 0.33 or more In addition, the refractive index of a cured film obtained by using a composition in which a metal fluoride is dispersed can be further reduced to 3 or less, and the refractive index can be further lowered than the theoretical refractive index.

2) Examples 1 to Examples in which the total amount of the ring-containing (meth) acrylate and the ionic group-containing monomer with respect to the polymer containing an ethylenically unsaturated bond-containing monomer is 65% by mass or more 7 and Examples 9 to 16 showed a lower refractive index and a higher refractive index difference than Example 8 in which the total amount was 60% by mass.

From this, it can be seen that if the total amount of the ring-containing (meth) acrylate and the ionic group-containing monomer with respect to the polymer of the ethylenically unsaturated bond-containing monomer is 65% by mass or more, it can be further improved. The refractive index of a cured film obtained by using a composition in which a metal fluoride is dispersed can be reduced, and the refractive index of the cured film can be further lowered than the theoretical refractive index.

3) Examples 1 to 7 and Examples 9 to 16 having a glass transition temperature of 70 ° C or higher and 180 ° C or lower of a polymer containing an ethylenically unsaturated bond, and the above-mentioned glass transition temperature is 56 ° C. Compared with Example 8, it showed a lower refractive index and a higher refractive index difference.

From this, it can be seen that if the glass transition temperature of the polymer containing an ethylenically unsaturated bond-containing monomer is 70 ° C or higher and 180 ° C or lower, the refractive index of a cured film obtained by using a composition in which metal fluoride is dispersed can be further reduced The rate can be lowered further than the theoretical refractive index.

4) Example 1 (8.3 nm) with an average particle diameter of 1 nm to 10 nm of the metal fluoride showed a lower refractive index and higher refractive index than Example 16 with an average particle diameter of 22.1 nm. Rate difference.

From this, if the average particle diameter of the metal fluoride is 1 nm or more and 10 nm or less, the refractive index of the cured film obtained by using the composition in which the metal fluoride is dispersed can be further reduced, and the refractive index can be further lowered than the theoretical refractive index. .

5) Example 1 (9% by mass) of the solids ratio of the polymer with respect to the total amount of the solids of the monomer containing the ethylenically unsaturated bond and the solid content of the metal fluoride ) Shows a lower refractive index and a higher refractive index difference than Example 15 in which the above-mentioned blending ratio is 13% by mass.

From this, it can be seen that if the solid content ratio of the polymer with respect to the total solid content of the polymer containing the ethylenically unsaturated bond-containing monomer and the metal fluoride is 5 mass% or more and 10 mass% or less, it can be further reduced. The refractive index of a cured film obtained by using a composition in which a metal fluoride is dispersed can be further lowered than the theoretical refractive index.

6) The blending ratio (Y) of the ring-containing (meth) acrylic ester and the blending ratio of the ionic group-containing monomer (X) in Examples 1 to 12 and Comparative Examples 1 and 2 are shown (X The graph of the relationship between) is shown in FIG. 1.

At this time, it can be seen that the blending ratio (Y) of the (meth) acrylate of the refractive index of the cured film obtained by using the composition in which metal fluoride is dispersed can be further reduced (X) The relationship between) (area (the oblique line in FIG. 1)) is determined by the relationship formula (Y ≧ 0.33X, Y ≦ 3X, X + Y ≧ 65, and X + Y ≦ 100) in FIG. 1.

In detail, Examples 1 to 7 and Examples 9 to 12 included in the above-mentioned area show a comparatively high comparison with Examples 8, Comparative Examples 1, and 2 not included in the above-mentioned area. Low refractive index and higher refractive index difference.

The above invention is provided in the form of an exemplary embodiment of the present invention, but it is only an example and is not to be construed in a limited manner. Modifications of the present invention, as will be apparent to those skilled in the art, are included in the scope of patent application to be described later.

    (Industrial availability)    

The metal fluoride-dispersed composition of the present invention is used to form a cured film. Moreover, this cured film is used for various optical related members, such as a laminated glass intermediate layer, for example. This laminated glass intermediate layer is used for producing laminated glass.

Claims (8)

    A metal fluoride-dispersed composition, which is characterized in that it contains a polymer containing an ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium. The single system containing the ethylenic unsaturated bond includes a ring-containing structure. Mass ratio of the (meth) acrylic acid ester and ionic group-containing monomer, the ring-containing (meth) acrylic acid ester to the ionic group-containing monomer (ring-containing (meth) acrylic acid) Ester / ionic group-containing monomer) is 0.33 or more and 3 or less.         For example, the metal fluoride-dispersed composition according to claim 1, wherein the ring-containing (meth) acrylate and the ionic group-containing The total amount of monomers is 65% by mass or more.         The metal fluoride-dispersed composition according to claim 1, wherein the glass transition temperature of the polymer is 70 ° C or higher and 180 ° C or lower.         The metal fluoride-dispersed composition according to claim 1, wherein the average particle diameter of the metal fluoride is 1 nm or more and 10 nm or less.         For example, the composition containing metal fluoride dispersed in claim 1, wherein the solid content ratio of the polymer is 5 mass% or more and 10 mass% or less with respect to the total solid content of the polymer and the metal fluoride.         The metal fluoride-dispersed composition as claimed in claim 1 is a low refractive index coating agent.         A cured film comprising a cured product of a composition in which a metal fluoride is dispersed, according to claim 1.         A laminated glass intermediate layer, comprising: a cured film according to claim 7.