JPWO2018181154A1 - Metal fluoride dispersion composition, solidified film, and laminated glass interlayer - Google Patents

Abstract

The metal fluoride dispersion 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 (the ring structure-containing (meth) ) / Acrylate / ionic group-containing monomer) is 0.33 or more and 3 or less.

Description

  The present invention relates to a metal fluoride dispersion composition, a solidified film, and a laminated glass intermediate layer, and more particularly, to a metal fluoride dispersion composition, a solidified film containing a solidified product of the metal fluoride dispersion composition, and the solidification thereof. It relates to a laminated glass interlayer comprising a membrane.

  Conventionally, low refractive index fine particles are dispersed in a resin composition used as a coating material in order to lower the refractive index of a solidified film formed by applying and solidifying the resin composition.

  As such low refractive index fine particles, for example, metal fluoride is known.

  As a resin composition containing such low refractive index fine particles, for example, a resin composition containing a carboxyl group-containing (meth) acrylate, a polyfunctional acrylate having three or more acryloyl groups in a molecule, and magnesium fluoride A product has been proposed (for example, see Patent Document 1 below).

JP-A-8-244178

  In recent years, a lower refractive index than the solidified film of the resin composition of Patent Document 1 has been required.

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

  The present invention can lower the refractive index of the solidified film, and, to obtain a solidified film having a lower refractive index than the theoretical refractive index, a metal fluoride dispersion composition, solidifying the metal fluoride dispersion composition. An object of the present invention is to provide an obtained solidified film and a laminated glass intermediate layer including the solidified film.

  The present invention [1] includes a polymer of an ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium, wherein the ethylenically unsaturated bond-containing monomer includes a ring structure-containing (meth) acrylate; An ionic group-containing monomer, and the mass ratio of the ring structure-containing (meth) acrylate to the ionic group-containing monomer (ring structure-containing (meth) acrylate / ionic group-containing monomer) is 0.33 or more and 3 or more. The following is a metal fluoride dispersion composition.

  The present invention [2], wherein the total amount of the (meth) acrylate and the ionic group-containing monomer is 65% by mass or more based on the total amount of the ethylenically unsaturated bond-containing monomer. It contains the metal fluoride dispersion composition described.

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

  The present invention [4] includes the metal fluoride dispersion composition according to any one of the above [1] to [3], wherein the metal fluoride has an average particle diameter of 1 nm or more and 10 nm or less. .

  The present invention [5], wherein the solid content ratio of the polymer to the total solid content of the polymer and the metal fluoride is 5% by mass or more and 10% by mass or less. ] The metal fluoride dispersion composition according to any one of the above items is included.

  The present invention [6] includes the metal fluoride dispersion composition according to any one of the above [1] to [5], which is a low refractive index coating agent.

  The present invention [7] includes a solidified film containing a solidified product of the metal fluoride dispersion composition according to any one of the above [1] to [5].

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

  In the metal fluoride dispersion composition of the present invention, the ethylenically unsaturated bond-containing monomer contains a polymer of an ethylenically unsaturated bond-containing monomer containing a ring structure-containing (meth) acrylate and an ionic group-containing monomer. The mass ratio (ring structure-containing (meth) acrylate / ionic group-containing monomer) of the ring structure-containing (meth) acrylate to the ionic group-containing monomer is 0.33 or more and 3 or less. Therefore, the refractive index of the solidified film can be made lower, and can be made lower than the theoretical refractive index.

  The solidified film of the present invention including the solidified product of the metal fluoride dispersion composition of the present invention has a lower refractive index and has a lower refractive index than the theoretical refractive index. Therefore, when the laminated glass intermediate layer includes this solidified film, the refractive index of the laminated glass intermediate layer can be made lower and can be made lower than the theoretical refractive index.

  The interlayer of the laminated glass including the solidified film of the present invention has a lower refractive index and has a lower refractive index than the theoretical refractive index. Therefore, the laminated glass intermediate layer has excellent antireflection properties.

FIG. 1 shows the mixing ratio (Y) of the ring-structure-containing (meth) acrylate and the mixing ratio (X) of the ionic group-containing monomer in Examples 1 to 12 and Comparative Examples 1 and 2. It is a graph which shows a relationship.

  The metal fluoride dispersion composition of the present invention contains a polymer of an ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium. More specifically, in the metal fluoride dispersion composition of the present invention, a polymer of an ethylenically unsaturated bond-containing monomer and a metal fluoride are dispersed in a dispersion medium. The polymer of the ethylenically unsaturated bond-containing monomer is a dispersant for dispersing the metal fluoride in the dispersion medium.

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

  When the ethylenically unsaturated bond-containing monomer contains the ring structure-containing (meth) acrylate, the steric hindrance caused by the ring structure-containing (meth) acrylate improves the dispersibility of the metal fluoride. Further, since the ethylenically unsaturated bond-containing monomer contains the ionic group-containing monomer, the dispersibility of the metal fluoride is improved by the affinity between the ionic group-containing monomer and the metal fluoride. And since the ethylenically unsaturated bond-containing monomer contains both the ring structure-containing (meth) acrylate and the ionic group-containing monomer, the actions of both combine to further improve the dispersibility of the metal fluoride.

  The ring structure-containing (meth) acrylate is an acrylate and / or methacrylate having a ring structure, for example, a (meth) acrylate having an alicyclic group containing one alicyclic ring, and an acrylate containing two or more alicyclic rings. A (meth) acrylate having a cyclic group, a (meth) acrylate having an aromatic group, and the like can be given.

  Examples of the (meth) acrylate having an alicyclic group containing one alicyclic ring include, for example, cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and cycloheptyl (meth) acrylate. A) acrylate, cyclooctyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, n-butylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dimethylcyclohexyl (meth) acrylate, cyclo Hexenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, and the like are included.

  Examples of the (meth) acrylate having an alicyclic group containing two or more alicyclic groups include, for example, bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and adamantyl methyl ( (Meth) acrylate, 2-methyladamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, bicyclo [4.4.0] decanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Tricyclopentanyl (meth) acrylate, tricyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 2-[(2,4-cyclopentyl) Dienyl) oxy] ethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate And the like.

  Examples of the (meth) acrylate having an aromatic group include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Phenoxy polypropylene glycol (meth) acrylate, biphenyl (meth) acrylate, ethoxylated ortho-phenylphenol (meth) acrylate, and the like.

  The ring structure-containing (meth) acrylate is preferably a (meth) acrylate having an alicyclic group containing two or more alicyclic rings, from the viewpoint of improving the effect of steric hindrance between metal fluorides. Is bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, more preferably isobornyl (meth) acrylate, adamantyl (meth) acrylate, and particularly preferably isobornyl methacrylate , Adamantyl acrylate, most preferably isobornyl methacrylate.

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

  Examples of the ionic group-containing monomer include, for example, anionic monomers such as a carboxyl group-containing monomer and a phosphate group-containing monomer, such as a tertiary amino group-containing monomer, such as a cationic monomer such as a quaternary ammonium group-containing monomer. No.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid), for example, α, β-unsaturated carboxylic acid such as itaconic acid, maleic acid, and fumaric acid, or a salt thereof; For example, a half esterified product of a hydroxyalkyl (meth) acrylate and an acid anhydride may be mentioned.

  Examples of the phosphoric acid group-containing monomer include phosphoric acid group-containing (meth) acrylates such as acid phosphooxyethyl (meth) acrylate and mono (2-hydroxyethyl (meth) acrylate) phosphate. (2-hydroxyethyl (meth) acrylate) phosphate.

  Examples of the tertiary amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N- N, N-dialkylaminoalkyl (meth) acrylates such as di-t-butylaminoethyl (meth) acrylate and N, N-dimethylaminobutyl (meth) acrylate, for example, N, N-dimethylaminoethyl (meth) acrylamide , N, N-diethylaminoethyl (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide, and the like, preferably N, N-dialkylamino Alkyl (meth) acrylate Preferably, N, N-dimethylaminoethyl (meth) acrylate, more preferably, N, N-dimethylaminoethyl methacrylate.

  The quaternary ammonium group-containing monomer is, for example, one obtained by allowing a quaternizing agent (e.g., epihalohydrin, benzyl halide, alkyl halide, etc.) to act on the above tertiary amino group-containing monomer. For example, (meth) acryloyloxyalkyltrialkylammonium salts such as 2- (methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, and 2- (methacryloyloxy) ethyltrimethylammonium dimethyl phosphate; (Meth) acryloylaminoalkyltrialkylammonium such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide Umushio, for example, tetraalkyl (meth) acrylates such as tetrabutylammonium (meth) acrylate, for example, trialkyl benzyl ammonium (meth) acrylates such as trimethylbenzylammonium (meth) acrylate.

  As the ionic group-containing monomer, usually from the viewpoint of improving the affinity to the metal fluoride surface having hydrophilicity, from the viewpoint of improving the affinity, preferably an anionic monomer, more preferably, a carboxyl group-containing monomer, further preferably, particularly Preferably, (meth) acrylic acid, furthermore, methacrylic acid is used.

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

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

  The copolymerizable monomer (excluding the ring structure-containing (meth) acrylate and the ionic group-containing monomer) is a monomer copolymerizable with the ring structure-containing (meth) acrylate and the ionic group-containing monomer, and includes, for example, an alkyl ( Examples include meth) acrylates, styrenes, monomers having a reactive functional group, maleic esters such as dimethyl maleate, fumaric esters such as dimethyl fumarate, acrylonitrile, methacrylonitrile, and vinyl acetate. In addition, the alkyl (meth) acrylate includes an alkyl acrylate and / or an alkyl methacrylate.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) ) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Rate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyltridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), isostearyl (meth) acrylate, C1-C30 linear or branched alkyl (meth) acrylates such as eicosyl (meth) acrylate, docosyl (meth) acrylate (behenyl (meth) acrylate), tetracosyl (meth) acrylate, and triacontyl (meth) acrylate And preferably a straight-chain alkyl (meth) acrylate having 1 to 30 carbon atoms, more preferably a straight-chain alkyl (meth) acrylate having 2 to 4 carbon atoms, and still more preferably n-butyl (meth) Acrylate, isobutyl (meth) acrylate.

  Examples of the styrenes include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene and the like, and preferably styrene.

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

  The isocyanate group-containing monomer has an isocyanate group as a reactive functional group, and includes, for example, isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 1- Methyl-2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate and the like can be mentioned.

  The hydroxyl group-containing monomer has a hydroxyl group as a reactive functional group. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and preferably, 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate And more preferably, 2-hydroxyethyl acrylate and 3-hydroxypropyl methacrylate.

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

  From the viewpoint of adjusting the glass transition temperature (described below) of the polymer of the ethylenically unsaturated bond-containing monomer, the copolymerizable monomer is preferably a styrene, a reactive functional group-containing monomer, and more preferably a hydroxyl group-containing monomer. Monomers, styrene, more preferably, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and styrene are exemplified.

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

  In addition, the reactive functional group derived from the reactive functional group-containing monomer can react with an active energy ray-curable group-containing monomer (described later).

  The mixing ratio of the ring structure-containing (meth) acrylate is based on the total amount of the ethylenically unsaturated bond-containing monomer (that is, the total amount of the ring structure-containing (meth) acrylate, the ionic group-containing monomer, and the copolymerizable monomer). For example, it is 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 75% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.

  When the compounding ratio of the ring structure-containing (meth) acrylate is within the above range, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be lowered, and the theoretical refractive index (described later) ) Can be lower.

  The mixing ratio of the ionic group-containing monomer is, for example, 16.25% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, based on the total amount of the ethylenically unsaturated bond-containing monomer. It is preferably at least 35% by mass, and for example, at most 75% by mass, preferably at most 65% by mass, more preferably at most 55% by mass, even more preferably at most 45% by mass.

  When the compounding ratio of the ionic group-containing monomer is within the above range, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be made lower, and the theoretical refractive index (described later) Can be even lower.

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

  When the compounding ratio of the ionic group-containing monomer is 29% by mass or more and less than 55% by mass, the compounding ratio of the ring-structure-containing (meth) acrylate is, for example, 35% by mass or more, preferably 40% by mass or more. And, for example, less than 60% by mass, preferably 55% by mass or less.

  Further, when the compounding ratio of the ionic group-containing monomer is 55% by mass or more and 70% by mass or less, the compounding ratio of the ring-structure-containing (meth) acrylate is, for example, 20% by mass or more and less than 35% by mass.

  That is, when the compounding ratio of the ionic group-containing monomer is small, the compounding ratio of the ring structure-containing (meth) acrylate is increased, and when the compounding ratio of the ionic group-containing monomer is large, the ring structure is used. By reducing the blending ratio of the contained (meth) acrylate, the refractive index of the solidified film (described later) obtained using the metal fluoride dispersion composition can be lowered, and further, lower than the theoretical refractive index (described later). it can.

  The mass ratio of the ring structure-containing (meth) acrylate to the ionic group-containing monomer (ring structure-containing (meth) acrylate / ionic group-containing monomer) is 0.33 or more, preferably 0.50 or more, It is preferably at least 0.80, more preferably at least 1.0, and for example, at most 3.0, preferably at most 2.3, more preferably at most 1.5.

  When the mass ratio is equal to or greater than the lower limit or equal to or less than the upper limit, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be lowered, and the theoretical refractive index (described later) ) Can be lower.

  On the other hand, if the mass ratio is less than the lower limit or exceeds the upper limit, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition is equal to or more than the lower limit or the above. Is higher than the case where it is equal to or less than the upper limit of.

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

  When the total amount of the ring structure-containing (meth) acrylate and the ionic group-containing monomer is at least the lower limit described above, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be lowered, and , Can be made even lower than the theoretical refractive index (described later).

The compounding ratio (Y) of the ring structure-containing (meth) acrylate and the compounding ratio (X) of the ionic group-containing monomer preferably satisfy the following formulas (1) to (4).
Y ≧ 0.33X (1)
Y ≦ 3X (2)
X + Y ≧ 65 (3)
X + Y ≦ 100 (4)
Specifically, the above equations (1) to (4) are obtained by the examples described later.

  If the compounding ratio of the ring structure-containing (meth) acrylate and the compounding ratio of the ionic group-containing monomer satisfy the above formulas (1) to (4), the solidified film obtained by using the metal fluoride dispersion composition ( (To be described later) can be further reduced, and can be further lowered than a theoretical refractive index (to be described later).

  The copolymerizable monomer is the remainder of the ring structure-containing (meth) acrylate and the ionic group-containing monomer. Specifically, the mixing ratio of the copolymerizable monomer is based on the total amount of the ethylenically unsaturated bond-containing monomer. Thus, for example, 0.1% by mass or more, preferably 5% by mass or more, and for example, 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, particularly preferably , 25% by mass or less, and even 20% by mass or less.

  When the compounding ratio of the copolymerizable monomer is equal to or less than the above upper limit, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be further reduced, and the theoretical refractive index (described later) Can be even lower.

  The polymer of such an ethylenically unsaturated bond-containing monomer is not particularly limited. For example, the above-mentioned monomer component (ring-structure-containing (meta) is prepared by a known polymerization method such as bulk polymerization, solution polymerization, or suspension polymerization. Acrylate, ionic group-containing monomer and copolymerizable monomer). Preferably, the polymer of the monomer containing an ethylenically unsaturated bond is obtained by solution polymerization.

  In the solution polymerization, a polymerization initiator and the like are compounded in a solvent together with the above-mentioned monomer components to carry out polymerization.

  The polymerization initiator is not particularly limited, and is appropriately selected depending on the purpose and application, and includes, for example, a known radical polymerization initiator.

  Examples of the radical polymerization initiator include azo compounds, peroxide compounds, sulfides, sulfines, sulfinic acids, diazo compounds, redox compounds, and the like, and preferably azo compounds.

  Examples of the azo compound include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl 2,2′-azo Bisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methylbutyronitrile) and the like can be mentioned, preferably 2,2'-azobis (2-methylbutyrate). Lonitrile).

  The mixing ratio of the polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, based on 100 parts by mass of the total amount of the ethylenically unsaturated bond-containing monomer, and, for example, 13 parts by mass. Or less, 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 to the above-mentioned monomer components, and examples thereof include an organic solvent and an aqueous solvent.

  As the organic solvent, for example, hexane, petroleum hydrocarbon solvents such as mineral spirits, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc. Ketone solvents such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, ester solvents such as propylene glycol monomethyl ether acetate, for example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide; Aprotic polar solvents such as N-methylpyrrolidone and pyridine;

  Examples of the aqueous solvent include water, for example, alcohol 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 is also available as a commercial product, and specific examples of the petroleum-based hydrocarbon solvent include, for example, AF Solvent Nos. 4 to 7 (all manufactured by Nippon Oil Co., Ltd.). Examples of the hydrocarbon-based solvent include Ink Solvent 0, Solvesso 100, 150, and 200 manufactured by Exxon Chemical Co., Ltd. (all manufactured by Nippon Oil Co., Ltd.).

  The mixing ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and use.

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

  The polymerization conditions in the solution polymerization are different depending on the type of the monomer component, the polymerization initiator, and the solvent, but the polymerization temperature is, for example, 30 ° C. or higher, preferably 60 ° C. or higher, For example, 150 ° C. or less, preferably 120 ° C. or less, and the polymerization time is, for example, 2 hours or more, preferably 4 hours or more, and, for example, 20 hours or less, preferably 8 hours or less. It is.

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

  Further, when the metal fluoride dispersion composition containing the polymer of the ethylenically unsaturated bond-containing monomer is solidified (cured) by light irradiation, the above-mentioned reactive functional group in the polymer of the ethylenically unsaturated bond-containing monomer is used. An activity having a reactive functional group derived from a group-containing monomer and / or an ionic group derived from the above-mentioned ionic group-containing monomer, and a reactive functional group capable of reacting with the reactive functional group and / or the ionic group The polymer is reacted with the energy ray-curable group-containing monomer to modify the polymer of the ethylenically unsaturated bond-containing monomer.

  The active energy ray-curable group-containing monomer is a reactive functional group derived from the reactive functional group-containing monomer and / or a reactive functional group capable of reacting with the ionic group derived from the ionic group-containing monomer. Having an active energy ray-curable group.

  The active energy ray-curable group is a functional group containing an ethylenic double bond that shows curability upon irradiation with an active energy ray, and specific examples include a (meth) acryloyl group. In addition, (meth) acryloyl includes acryloyl and methacryloyl.

  As an active energy ray-curable group-containing monomer, for example, as a reactive functional group, an isocyanate group-containing monomer having an isocyanate group that is a functional group capable of binding to a hydroxyl group, for example, as a reactive functional group, a glycidyl group A carboxyl group-containing monomer having a carboxyl group that is a functional group capable of binding to the compound, for example, a hydroxyl group-containing monomer having a hydroxyl group that is a functional group capable of binding to an isocyanate group as a reactive functional group, for example, a reaction As a reactive functional group, a glycidyl group-containing monomer having a glycidyl group that is a functional group capable of binding to a carboxyl group and a phosphate group, for example, a functional group capable of binding to a glycidyl group as a reactive functional group Phosphoric acid group-containing monomers having a phosphoric acid group .

  Examples of the isocyanate group-containing monomer, the hydroxyl group-containing monomer, and the glycidyl group-containing monomer include the same monomers as those exemplified above as the copolymerizable monomer.

  Examples of the carboxyl group-containing monomer and the phosphoric acid group-containing monomer include the same monomers as those exemplified above for the ionic group-containing monomer.

  The compounding ratio of the active energy ray-curable group-containing monomer is, for example, 1% by mass or more, preferably 3% by mass or more, for example, 66% by mass or less, based on the total amount of the ethylenically unsaturated bond-containing monomer. Preferably, it is at most 50% by mass, more preferably at most 35% by mass, further preferably at most 20% by mass, particularly preferably at most 15% by mass.

  In the case where an ionic group derived from the ionic group-containing monomer is reacted with a reactive functional group derived from the active energy ray-curable group-containing monomer, an ionic group derived from the ionic group-containing monomer is used, While reacting with the reactive functional group derived from the active energy ray-curable group-containing monomer, it is blended so as to adjust the mass ratio of the ionic group-containing monomer that does not contribute to the reaction and the ring structure-containing (meth) acrylate.

  Specifically, the mass ratio of the ring-structure-containing (meth) acrylate to the ionic-group-containing monomer (the ionic-group-containing monomer that does not contribute to the reaction) (the ring-structure-containing (meth) acrylate / ionic-group-containing monomer ( The ionic group-containing monomer which does not contribute to the reaction)) is blended in the above-mentioned range.

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

  Thereby, the polymer of the monomer having 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, the metal fluoride dispersion composition containing such a polymer of the ethylenically unsaturated bond-containing monomer can be solidified (cured) 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 even more preferably 100 ° C. or higher. C. or lower, preferably 180 ° C. or lower, more preferably 160 ° C. or lower.

  If the glass transition temperature of the polymer of the ethylenically unsaturated bond-containing monomer is at least the lower limit described above, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be lowered, and It can be much lower than the theoretical refractive index (described later).

  When the glass transition temperature of the polymer of the monomer containing an ethylenically unsaturated bond is equal to or less than the above upper limit, a solidified film obtained using the metal fluoride dispersion composition has excellent flexibility.

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

  The polymer of the ethylenically unsaturated bond-containing monomer, the weight average molecular weight in terms of polyethylene styrene by gel permeation chromatography is, for example, 500 or more, preferably 3000 or more, and, for example, 20,000 or less, preferably, It is 10,000 or less.

  The metal fluoride is dispersed in the metal fluoride dispersion composition in order to lower the refractive index of a solidified film obtained using the metal fluoride dispersion 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, barium fluoride and the like.

  Preferably, the metal fluoride is an alkaline earth metal fluoride, more preferably, 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 still more preferably. Is 12 nm or less, particularly preferably 10 nm or less.

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

  When the average particle diameter of the metal fluoride is equal to or less than the above upper limit, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be made lower, and the theoretical refractive index (described later) can be reduced. Can be even lower. Further, smoothness can be improved.

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

  The ratio of the solid content of the polymer of the ethylenically unsaturated bond-containing monomer to the total amount of the solid content of the polymer of the ethylenically unsaturated bond-containing monomer and the metal fluoride is 5.0% by mass or more, preferably, 7. It is 0% by mass or more, and for example, 30% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less.

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

  When the above-mentioned solid content ratio is equal to or less than the above-mentioned upper limit, the refractive index of a solidified film (described later) obtained using the metal fluoride dispersion composition can be made lower, and it is further higher than the theoretical refractive index (described later). Can be lowered.

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

  The dispersion medium is a liquid in which the metal fluoride is dispersed, and includes, for example, the above-described solvents used when polymerizing a polymer of an ethylenically unsaturated bond-containing monomer by solution polymerization.

  From the viewpoint of improving the working efficiency, when the polymer of the monomer having an ethylenically unsaturated bond is subjected to solution polymerization, preferably, the solvent used at that time is used as it is as the dispersion medium.

  As the dispersion medium, an aqueous solvent is preferable, and a glycol ether solvent is more preferable.

  The mixing ratio of the dispersion medium is, for example, 1% by mass or more, preferably 3% by mass or more, and for example, 99% by mass or less, preferably 95% by mass or less, based on the metal fluoride dispersion composition. It is.

  Although such a metal fluoride dispersion composition is not particularly limited, for example, a polymer of the above-mentioned ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium are blended, and then, the ethylenically unsaturated It is obtained by dispersing a polymer of a bond-containing monomer and a metal fluoride 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 known paint shakers, roll mills, ball mills, attritors, sand mills, bead mills, and ultrasonic dispersers. A method of dispersing using a dispersing machine is preferred. From the viewpoint of improving coatability, paint stability, and transparency of a solidified film (described later), preferably a ball mill, a bead mill, and more preferably a bead mill Is mentioned.

  When a bead mill is used as a dispersing machine, known dispersion media such as zirconia beads and glass beads can be used.

  The bead diameter of the dispersion medium is not particularly limited, but is, for example, 10 μm or more, and is, for example, 500 μm or less, preferably 100 μm or less. Note that the filling rate of the dispersion medium is appropriately set according to the purpose and use.

  When a bead mill or a ball mill is used as the dispersing machine, the metal fluoride can be pulverized with the above-mentioned dispersing medium, and the average particle diameter can be adjusted to the above range. In such a case, a metal fluoride having an average particle diameter larger than the above range can be blended in the disperser.

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

  Further, the metal fluoride dispersion composition can contain a polymerizable compound (curing agent) such as a polyfunctional acrylate or a polyfunctional isocyanate, a known additive, and the like. When the metal fluoride dispersion composition contains a polymerizable compound, the metal fluoride dispersion composition is cured by light irradiation or heating.

  As a result, a metal fluoride dispersion composition containing the polymer of the ethylenically unsaturated bond-containing monomer, the metal fluoride, and the dispersion medium is obtained.

  In such a metal fluoride dispersion composition, a polymer of an ethylenically unsaturated bond-containing monomer and a metal fluoride are dispersed by a dispersion medium.

  And this metal fluoride dispersion composition can be used as various coating agents (preferably low refractive index coating agents).

  The low-refractive-index coating agent is a coating agent capable of obtaining a solidified film having a low refractive index (described later), and is used for various optical members requiring a low refractive index.

  The low refractive index in the low refractive index coating agent means that the solidified film (described later) obtained using the low refractive index coating agent has a refractive index of less than 1.35, preferably 1.312 or less, and more preferably 1.312 or less. Means 1.297 or less, more preferably 1.285 or less, particularly preferably 1.283 or less, and more preferably 1.282 or less.

  Then, a solidified film can be obtained by applying the metal fluoride dispersion composition (coating agent) to the substrate and drying the dispersion medium.

  When an active energy ray-curable group is introduced into the side chain of the polymer of the monomer having an ethylenically unsaturated bond, or when the metal fluoride dispersion composition contains the above polymerizable compound, metal A solidified film (cured film) can be obtained by applying the fluoride dispersion composition to a substrate, drying the dispersion medium, and then performing light irradiation or heat curing.

  That is, the solidified film of the present invention contains the solidified product of the metal fluoride dispersion composition described above.

  The substrate is not particularly limited and includes, for example, polycarbonate, polymethyl methacrylate, polystyrene, polyester (such as polyethylene terephthalate), polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, and the like. Plastics, for example, metal, wood, paper, glass, slate and the like.

  The coating method is not particularly limited. For example, a roll coater, a spin coater, a bar coater, a doctor blade, a Meyer bar, an air knife, etc., at the time of coating, coating using a generally used device, or screen printing Known application methods such as offset printing, flexographic printing, brush coating, spray coating, gravure coating, and reverse gravure coating are employed.

  As the 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, it is 1 minute or more, and for example, 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 is, for example, 10 μm or less, preferably 7 μm or less.

  As a result, a solidified film containing the solidified metal fluoride dispersion composition is obtained.

  Such a solidified film has a lower refractive index because it contains a solidified product of the metal fluoride dispersion composition described above.

  Specifically, the refractive index of the solidified film is, for example, less than 1.35, preferably 1.312 or less, more preferably 1.297 or less, further preferably 1.285 or less, and particularly preferably 1 or less. .283 or less, and 1.282 or less.

  On the other hand, the refractive index of the solidified resin composition can be calculated as a theoretical refractive index using a Maxwell-Garnett model.

  Since the solidified film contains a solidified product of the metal fluoride dispersion composition described above, the solidified film has a lower refractive index than the theoretical refractive index calculated by the Maxwell-Garnett model.

  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, and 0.12 or more, particularly preferably. Is 0.131 or more, for example, 2 or less.

The Maxwell-Garnett model is a model for calculating the relative dielectric constant of a fine particle-dispersed resin in which a nano-size inclusion is dispersed in a matrix resin, and is represented by the following equation (5).

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

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

Relative dielectric constant = refractive index ² x relative magnetic permeability (6)
Since the relative magnetic permeability of a substance that is not a magnetic material is 1.0, the above equation (6) can be rewritten as the following equation (7).

Relative dielectric constant = refractive index ² (7)
Based on the above equation (7), the above equation (5) can be rewritten as the following equation (8).

In the above formula (8), _nav represents the refractive index of the fine particle-dispersed resin, specifically, the theoretical refractive index of a solidified film containing a solidified metal fluoride dispersion composition.

In the above formula (8), n _p indicates the refractive index of the nano-size inclusion, and specifically indicates the refractive index of the metal fluoride.

In the formula (8), n _m is the refractive index of the matrix resin, specifically, shows the polymer refractive index of the ethylenically unsaturated bond-containing monomer.

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

η = volume of nano-sized inclusion / (volume of matrix resin + volume of nano-sized inclusion) (9)
The volume of the nano-size inclusion and the volume of the matrix resin can be calculated by the following equations (10) and (11), respectively.

Volume of nano-sized inclusions = blending ratio of nano-sized inclusions / specific gravity of nano-sized inclusions (10)
Matrix resin volume = Matrix resin blending ratio / Matrix resin specific gravity (11)
In this way, a solidified film having a lower refractive index than the theoretical refractive index is obtained.

  Such a solidified film is useful for various optical-related members that require a low refractive index, and is particularly useful as a laminated glass intermediate layer.

  The laminated glass intermediate layer of the present invention includes the solidified film described above.

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

  Since this laminated glass intermediate layer includes the solidified film described above, it has a lower refractive index and has a lower refractive index than the theoretical refractive index. Therefore, the laminated glass intermediate layer has excellent antireflection properties.

  This laminated glass intermediate layer can be used for manufacturing laminated glass.

  The laminated glass is obtained, for example, by sandwiching a laminated glass intermediate layer between a pair of glass plates, and then pressing the pair of glass plates and the laminated glass intermediate layer using an autoclave and a press.

  Further, another resin layer other than the laminated glass intermediate layer may be interposed between the pair of glass plates.

  In such a case, the laminated glass intermediate layer can be sandwiched between the glass plate and another resin layer, or can be sandwiched between another resin layer and another resin layer. .

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

  Since such a laminated glass includes a laminated glass intermediate layer, it is excellent in antireflection properties.

  Such a laminated glass is used for various purposes, for example, as a windshield, a side glass, a rear glass of a vehicle such as an automobile, and a window glass of an aircraft, a building, and the like.

Specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the corresponding compounding ratios (content ratios) described in the above “Embodiment for carrying out the invention”. ), Physical property values, parameters, etc., may be replaced with the upper limit (the value defined as “less than” or “less than”) or the lower limit (the value defined as “greater than” or “exceeding”) it can. In the following description, “parts” and “%” are based on mass unless otherwise specified.
1. Production of polymer of ethylenically unsaturated bond-containing monomer (Synthesis Example 1)
100 parts of propylene glycol monomethyl ether (PGME) was placed in a flask equipped with a stirrer, a condenser, a thermometer, an inert gas inlet tube and a dropping funnel, an inert gas (nitrogen gas) was introduced, and the temperature was raised to 110 ° C. . Thereafter, using a dropping funnel with stirring, 50 parts of isobornyl methacrylate as a (meth) acrylate containing a ring structure, 40 parts of methacrylic acid as a monomer containing an ionic group, 9.7 parts of styrene as a copolymerizable monomer, Consists of 0.1 part of isobutyl methacrylate, 0.1 part of 2-hydroxyethyl acrylate, 0.1 part of 3-hydroxypropyl methacrylate, and 8 parts of 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator The mixture was added dropwise over 2 hours. One hour later, 2 parts of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator, and the mixture was reacted for 3 hours. Thus, a polymer of an ethylenically unsaturated bond-containing monomer was obtained.

(Synthesis Example 2 to Synthesis Example 16)
The same treatment as in Synthesis Example 1 was carried out except that the formulation was changed as described in Table 1, to obtain a polymer of an ethylenically unsaturated bond-containing monomer.
2. Production of metal fluoride dispersion composition and solidified film (Example 1)
9 parts of a polymer of the ethylenically unsaturated bond-containing monomer obtained in Synthesis Example 1 in terms of solid content, 91 parts of magnesium fluoride (manufactured by Central Glass, Magnesium Fluoride No. 4 (MgF ₂ )), and PGME809 as a solvent Parts, and 1500 parts of 50 μm zirconia beads as a dispersion medium are placed in a 300 mL bottle, and magnesium fluoride is pulverized at 60 Hz for 24 hours using a disperser (rocking shaker RS-05W manufactured by Seiwa Giken Co., Ltd.). And dispersed. Thereafter, the zirconia beads were removed by filtration to obtain a metal fluoride dispersion composition in which magnesium fluoride was dispersed. The solid content of the obtained metal fluoride dispersion composition was 11% by mass.

  Next, this metal fluoride dispersion composition is formed on a glass plate (2 mm, manufactured by Taiyo Kiki Co., Ltd.) using a spin coater, and the film thickness is measured using a reflection spectral thickness meter Fe-3000 (manufactured by Otsuka Electronics Co., Ltd.) The thickness was measured and the film was formed to have a thickness of 0.5 μm. Then, it dried and solidified at 80 degreeC for 1 minute, and the solidified film was obtained.

(Examples 2 to 16 and Comparative Examples 1 to 4)
The same treatment as in Example 1 was carried out except that the formulation and the dispersion time were changed as described in Table 2, to obtain a metal fluoride dispersion composition and a solidified film.

  In Comparative Example 3, silicon dioxide particles (Aerosil R812, manufactured by Evonik) were used in place of magnesium fluoride, and treated in the same manner as in Example 1 except that the modification was performed according to the description in Table 2. A composition and a solidified film were obtained.

In Comparative Example 4, Aronix M5300 (carboxyl polycaprolactone monoacrylate, manufactured by Toagosei Co., Ltd.) was used instead of the polymer of the monomer having an ethylenically unsaturated bond.
3. Evaluation 1) Average Particle Diameter For each of the metal fluoride dispersion compositions of Examples 1 to 16 and Comparative Examples 1 to 4, a laser diffraction / scattering particle size distribution analyzer Nanotrac UPA-EX150 (Nikkiso Co., Ltd.) Was measured under the following conditions. Table 2 shows the results.
Number of measurements: once Measurement time: 180 seconds Measurement temperature: 23 ° C
Average particle diameter: Value of cumulative 50% of volume average particle diameter Measurement solvent: CI value of dispersion medium used in preparing dispersion: 0.4 to 0.8
Particle permeability: Transmission sensitivity: Standard filter: Stand: Norm
2) Weight average molecular weight by gel permeation chromatography Each of the polymers of the ethylenically unsaturated bond-containing monomers of Synthesis Examples 1 to 16 was dissolved in tetrahydrofuran, and the sample concentration was adjusted to 1.0 g / L. Was measured by gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID) to obtain a molecular weight distribution of the sample.

Thereafter, the weight average molecular weight (Mw) of the sample was calculated from the obtained chromatogram (chart) using standard polystyrene as a calibration curve. The measuring device and the measuring conditions are shown below. The results are shown in Table 1.
Data processing device: Part number HLC-8220GPC (Tosoh Corporation)
Differential refractive index detector: Part number HLC-8220 RI detector built into GPC Column: Part number TSKgel SuperHZM-H (manufactured by Tosoh Corporation) Two mobile phases: Tetrahydrofuran column Flow rate: 0.35 mL / min
Sample concentration: 1.0 g / 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 (actually measured refractive index) of each solidified film of Examples 1 to 16 and Comparative Examples 1 to 4 was measured using a reflection spectral thickness meter Fe-3000 (manufactured by Otsuka Electronics Co., Ltd.). It measured using. Table 2 shows the results.

  Separately, the theoretical refractive index of each of the solidified films of Examples 1 to 16 and Comparative Examples 1 to 4 was calculated using the Maxwell-Garnett model.

Specifically, the refractive index (n _av ) (theoretical refractive index) of the solidified film of the metal fluoride dispersion composition was calculated using the above equations (8) to (11).

In Example 1, the refractive index (n _m ) of the polymer of the monomer containing an ethylenically unsaturated bond was 1.53, the refractive index (n _p ) of a metal fluoride was 1.38, and the content of the ethylenically unsaturated bond was The compounding ratio of the polymer of the monomer is 0.09, the compounding ratio of the metal fluoride is 0.91, the specific gravity of the polymer of the ethylenically unsaturated bond-containing monomer is 1.1, and the specific gravity of the metal fluoride is 3 .14, the theoretical refractive index was calculated. Table 2 shows the results.

The specific gravity of the polymer of the monomer having an ethylenically unsaturated bond and the specific gravity of Aronix M5300 were determined using a vibration type density / specific gravity meter DMA 4500M (manufactured by Anton Paar Japan).
From the linear approximation of the specific gravity value for each of the obtained concentrations (50%, 30%, 10%), the specific gravity of the polymer of the ethylenically unsaturated bond-containing monomer when the concentration (NV) was 100% was estimated. The measurement conditions are shown below.
Number of measurements: once for each concentration condition Concentration (NV): 50%, 30%, 10%
Diluent solvent: PGME
Measurement temperature: 23 ° C
The specific gravity of the metal fluoride used was 3.15 which is a specific gravity value of a known metal fluoride.

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

Next, the difference between the obtained theoretical refractive index and the obtained actually measured refractive index (theoretical refractive index-measured refractive index) (refractive index difference) was calculated. Table 2 shows the results.
4) Dispersibility Each metal fluoride dispersion composition of Examples 1 to 16 and Comparative Examples 1 to 4 was centrifuged using a centrifuge H-1500F manufactured by Kokusan Co., Ltd. The dispersibility of magnesium was confirmed visually. Table 2 shows the results. Evaluation of dispersibility was as follows.
A +: No sediment was observed when centrifuged at 10,000 rpm for 1 hour.
A: No sediment was observed when centrifuged at 5,000 rpm for 1 hour, and a sediment was observed when centrifuged at 10,000 rpm for 1 hour.
B: No sediment was observed when centrifuged at 2000 rpm for 1 hour, and no sediment was observed when centrifuged at 5000 rpm for 1 hour.
C: No sediment was observed when centrifuged at 500 rpm for 1 hour, and a sediment was observed when centrifuged at 2000 rpm for 1 hour.
D: Precipitate was observed before centrifugation.

4. Discussion 1) Examples 1 to 3 in which the mass ratio of the ring structure-containing (meth) acrylate to the ionic group-containing monomer (ring structure-containing (meth) acrylate / ionic group-containing monomer) is 0.33 or more and 3 or less. Example 16 shows a lower refractive index and a higher refractive index difference than Comparative Example 1 in which the above mass ratio is 3.29 and Comparative Example 2 in which the above mass ratio is 0.27.

From this, if the mass ratio of the ring structure-containing (meth) acrylate to the ionic group-containing monomer (ring structure-containing (meth) acrylate / ionic group-containing monomer) is 0.33 or more and 3 or less, the metal fluoride is used. It can be understood that the refractive index of the solidified film obtained by using the compound dispersion composition can be made lower and can be made lower than the theoretical refractive index.
2) Examples 1 to 7 and 9 in which the total amount of the ring structure-containing (meth) acrylate and the ionic group-containing monomer is 65% by mass or more based on the polymer of the ethylenically unsaturated bond-containing monomer. Nos. To 16 show a lower refractive index and a higher refractive index difference than Example 8 in which the total amount is 60% by mass.

From this, if the total amount of the ring structure-containing (meth) acrylate and the ionic group-containing monomer relative to the polymer of the ethylenically unsaturated bond-containing monomer is 65% by mass or more, the metal fluoride dispersion composition is used. It can be seen that the refractive index of the obtained solidified film can be made lower and can be made lower than the theoretical refractive index.
3) In Examples 1 to 7 and 9 to 16 in which the glass transition temperature of the polymer of the ethylenically unsaturated bond-containing monomer is 70 ° C. or more and 180 ° C. or less, the above glass transition temperature is , 56 ° C., a lower refractive index and a higher refractive index difference.

From this, if the glass transition temperature of the polymer of the ethylenically unsaturated bond-containing monomer is 70 ° C or higher and 180 ° C or lower, the refractive index of the solidified film obtained using the metal fluoride dispersion composition is lower. It can be seen that they can be made even lower than the theoretical refractive index.
4) Example 1 (8.3 nm), in which the average particle diameter of the metal fluoride is 1 nm or more and 10 nm or less, has a lower refractive index and a lower refractive index than Example 16 in which the average particle diameter is 22.1 nm. Shows a high refractive index 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 solidified film obtained by using the metal fluoride dispersion composition can be lower, and the refractive index is more than the theoretical refractive index. It can be seen that it can be lowered.
5) Example 1 (9% by mass) in which the solid content ratio of the polymer to the total amount of the solid content of the polymer of the ethylenically unsaturated bond-containing monomer and the metal fluoride is 5% by mass or more and 10% by mass or less. Shows a lower refractive index and a higher refractive index difference than Example 15 in which the above blending ratio is 13% by mass.

From this fact, if the solid content ratio of the polymer to the total amount of the polymer of the ethylenically unsaturated bond-containing monomer and the solid content of the metal fluoride is 5% by mass or more and 10% by mass or less, the metal fluoride dispersion It can be seen that the solidified film obtained by using the composition can have a lower refractive index and can have a lower refractive index than the theoretical refractive index.
6) The relationship between the compounding ratio (Y) of the ring-structure-containing (meth) acrylate and the compounding ratio (X) of the ionic group-containing monomer in Examples 1 to 12 and Comparative Examples 1 and 2 is as follows. The graph shown is shown in FIG.

  At this time, the relationship between the compounding ratio (Y) of the (meth) acrylate, which can lower the refractive index of the solidified film obtained using the metal fluoride dispersion composition, and the compounding ratio (X) of the ionic group-containing monomer ( It has been found that the area is defined by the area (shaded area in FIG. 1) and the relational expressions (Y ≧ 0.33X, Y ≦ 3X, X + Y ≧ 65, and X + Y ≦ 100) in FIG.

  Specifically, Examples 1 to 7 and Examples 9 to 12 included in the above-described region are compared with Examples 8, Comparative Examples 1 and 2, which are not included in the above-described region. It shows a low refractive index and a high refractive index difference.

  Note that the above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be construed as limiting. Modifications of the invention apparent to those skilled in the art are included in the following claims.

  The metal fluoride dispersion composition of the present invention is used for forming a solidified film. Further, the solidified film is used as various optical-related members such as a laminated glass intermediate layer. The laminated glass intermediate layer is used in the production of laminated glass.

Claims (8)

Containing a polymer of an ethylenically unsaturated bond-containing monomer, a metal fluoride, and a dispersion medium,
The ethylenically unsaturated bond-containing monomer includes a ring structure-containing (meth) acrylate and an ionic group-containing monomer,
The mass ratio of the ring structure-containing (meth) acrylate to the ionic group-containing monomer (ring structure-containing (meth) acrylate / ionic group-containing monomer) is 0.33 or more and 3 or less. Metal fluoride dispersion composition.   The metal according to claim 1, wherein the total amount of the (meth) acrylate and the ionic group-containing monomer is 65% by mass or more based on the total amount of the ethylenically unsaturated bond-containing monomer. Fluoride dispersion composition.   The metal fluoride dispersion composition according to claim 1, wherein the glass transition temperature of the polymer is 70C or more and 180C or less.   The metal fluoride dispersion composition according to claim 1, wherein the metal fluoride has an average particle diameter of 1 nm or more and 10 nm or less.   2. The metal fluoride according to claim 1, wherein a ratio of a solid content of the polymer to a total amount of the polymer and the solid content of the metal fluoride is 5% by mass or more and 10% by mass or less. Dispersion composition.   The metal fluoride dispersion composition according to claim 1, which is a low refractive index coating agent.   A solidified film comprising a solidified product of the metal fluoride dispersion composition according to claim 1.   A laminated glass intermediate layer, comprising the solidified film according to claim 7.

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