JP5171018B2 - Zirconium oxide-containing resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a resin composition containing at least a zirconium oxide component as an inorganic particle component and having high transparency (transparency to visible light) and a refractive index, and a molded article thereof.

  In recent years, in order to develop a new function in a resin material, a composite of a resin material and an inorganic material (for example, a metal oxide such as a metal oxide) has been studied. For example, JP-A No. 11-315249 (Patent Document 1) discloses a resin component, a solvent, and a transparent filler containing at least one selected from an acrylic compound and an epoxy compound having two or more epoxy groups as an essential component. For example, in a coating resin composition for forming a color filter protective film mainly composed of fine particles of barium sulfate, calcium carbonate, alumina, silica, etc., the transparent filler is coated with an epoxy resin, and the transparent filler 90% or more of the coating resin is dispersed with a particle diameter of less than or equal to the visible light wavelength, and a coating resin in which the light transmittance of a 2 μm-thick film obtained by forming this coating resin composition is 90% or more at a wavelength of 400 nm A composition is disclosed. This document exemplifies fluorene bisphenol epoxy (meth) acrylate as a preferred acrylic compound. However, in this resin composition, not only transparency is easily lowered by addition of a filler, but also it is difficult to improve hardness and refractive index.

Japanese Patent Laying-Open No. 2005-290199 (Patent Document 2) discloses (A) Formula (R ¹ O) _m M (OR ² ) _n (wherein R ¹ is capable of at least one radical polymerization. In the case where a plurality of R ¹ are present, they may be the same as or different from each other, and R ² represents a saturated hydrocarbon group having 1 to 5 carbon atoms. And a plurality of R ² may be the same or different from each other, and M represents at least one metal atom selected from the group consisting of Ti, Sb, W, Zr, Ce, Sn, and Fe. M and n each represent 0 or a natural number, provided that m and n are not 0 at the same time and the sum of m and n represents the valence of metal M) or a hydrolyzed compound thereof. And (B) (meth) a The photocurable resin composition containing the fluorene derivative having Riroiruokishi group is disclosed. However, in this document, the metal alkoxide is limited to a compound having a vinyl group capable of radical polymerization. Furthermore, when a titanium compound is used as the metal alkoxide to increase the refractive index, the resin composition is likely to be colored.

  Furthermore, in JP-A-2005-338550 (Patent Document 3), at least a hard coat layer, a layer having a higher refractive index than the transparent substrate film, and a refractive index higher than the transparent substrate film are provided on the transparent substrate film. In the antireflection film having a low layer, an antireflection film in which the layer having a higher refractive index than the transparent substrate film contains a polymer containing at least an acrylate compound or a methacrylate compound having a fluorene skeleton as a binder as a polymerization component is disclosed. ing. In this document, the layer having a higher refractive index than the transparent substrate film may contain metal oxide fine particles selected from Ti, Zr, Sn, etc., and such a metal oxide. It is described that the fine particles are preferably surface-treated with an inorganic compound (alumina, silica, zirconium oxide, etc.) or an organic compound (polyol, stearic acid, silane coupling agent, titanate coupling agent, etc.). However, even with the compositions described in these documents, it is difficult to improve the refractive index while increasing the hardness and transparency.

  On the other hand, in an organic-inorganic composite material, an attempt has been made to configure a resin component with a thermoplastic resin. For example, Japanese Patent Application Laid-Open No. 2003-292895 (Patent Document 4) discloses that a thermoplastic organic polymer contains 1 to 80% by weight of inorganic components (metal alkoxide, related compounds, and their hydrolytic condensation polymers). Hybrid materials blended in proportions and thermoplastic organic-inorganic hybrid materials are disclosed. In the method of this document, it is difficult to disperse the inorganic component with high dispersibility in the thermoplastic resin. Therefore, in the resin composition of this document, characteristics such as transparency tend to be lowered and haze tends to be increased.

JP-A-2004-339499 (Patent Document 5) discloses a composition containing a compound having a fluorene skeleton or a derivative thereof and an additive. In this document, a resin having a fluorene skeleton (polyester resin, polycarbonate resin, urethane resin, acrylic resin, etc.) is exemplified as the derivative, and a compound having a fluorene skeleton or a derivative thereof is used. Describes that the dispersibility of the additive can be improved, and the function of the additive can be expressed with a small amount of compounding.
JP 11-315249 A (claims, paragraph number [0025]) Japanese Patent Laying-Open No. 2005-290199 (Claims) JP 2005-338550 A (Claims, paragraph numbers [0161] and [0165]) Japanese Patent Laying-Open No. 2003-292895 (claims, paragraph number [0018]) JP 2004-339499 A (Claims)

  Accordingly, an object of the present invention is to provide a resin composition having high transparency and refractive index even when it contains a metal oxide component.

  Another object of the present invention is to provide a resin composition useful for obtaining a colorless and transparent molded article (such as a film) without coloring.

  Still another object of the present invention is to provide a resin composition useful for obtaining a molded body (such as a coating film) having high hardness, refractive index and transparency.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that a zirconium oxide component (or zirconium oxide particles or sol) having an average diameter of 30 nm or less (for example, an average particle diameter of 10 nm or less) as a main component of the inorganic particle component. In combination with a resin having a fluorene skeleton, it has been found that a resin composition having high transparency and refractive index and high hardness can be obtained without coloring despite containing inorganic particle components, The present invention has been completed.

  That is, the resin composition of the present invention comprises a base resin having a fluorene skeleton and an inorganic particle component containing at least a nanometer-sized zirconium oxide component (or a zirconium oxide component or fine particles having an average diameter of 30 nm or less as an inorganic component). ing. The average diameter of the zirconium oxide component may be 10 nm or less (for example, about 0.3 to 7 nm). Such zirconium oxide is a zirconium oxide component composed of a hydrolysis-condensable zirconium compound, and may be a hydrolysis-condensation product (zirconium oxide sol) of the condensation component. The proportion of the zirconium oxide component in the inorganic particle component may be about 30 to 100% by weight. Further, the base resin may be a photopolymerizable resin having a fluorene skeleton. More specifically, the resin composition may contain a (meth) acrylate having a fluorene skeleton and a zirconium oxide component having an average particle size of 0.3 to 10 nm, and is based on 100 parts by weight of the (meth) acrylate. The proportion of the zirconium oxide component may be about 3 to 400 parts by weight.

  The present invention may be combined with other inorganic particle components (such as metal oxide components) as long as they contain a zirconium oxide component. Moreover, the molded object formed with the said composition is also included. This molded body has high transparency (transparency to visible light) and a refractive index. The refractive index of the molded body may be, for example, about 1.6 to 1.85. Moreover, the molded body is less colored and a colorless and transparent molded body can be easily obtained.

  In the resin composition of the present invention, since the type of resin (resin having a fluorene skeleton) and the type of metal particle component are selected and combined, even if it contains a zirconium oxide component, it has excellent transparency and high transparency. Can be realized. Furthermore, in the present invention, a resin composition having a high transparency and a high refractive index with little coloring can be provided by using a zirconium oxide component as a main component as a resin having a fluorene skeleton and / or an inorganic particle component. Moreover, a molded object (a film etc.) with high hardness, refractive index, and transparency can also be obtained.

  The resin composition of the present invention is composed of a base resin having a fluorene skeleton and a zirconium oxide component as an inorganic particle component, and the inorganic particle component contains a zirconium oxide component as a main component.

[Base resin]
As long as the base resin has a fluorene skeleton (fluorene-9,9-diyl skeleton such as 9,9-bisarylfluorene), various resins (thermoplastic resins including thermoplastic resins and photo-curable resins) can be used. The base resin is not limited to a high molecular weight resin and may be an oligomer. A resin having such a fluorene skeleton has high affinity and dispersibility for the zirconium oxide component. Therefore, the zirconium oxide component does not necessarily need to be surface treated.

  The resin having a fluorene skeleton may be a resin using a compound represented by the following formula (sometimes simply referred to as a fluorene compound) as a monomer component.

(In the formula, rings Z ¹ and Z ² are the same or different and represent an aromatic hydrocarbon ring, and R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or a reactive group. K 1 and k 2 are the same. Or an integer of 1 or more differently, and m1 and m2 are the same or different and represent 0 or an integer of 1 to 4)
In the above formula (1), the aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² may be either a non-condensed ring or a condensed ring. For example, a benzene ring, an indene ring, a naphthalene ring And C _6-20 aromatic hydrocarbon rings (preferably C _6-14 aromatic hydrocarbon rings) such as anthracene ring. Among these hydrocarbon rings, C _6-10 aromatic hydrocarbon rings such as a benzene ring and a naphthalene ring are preferable. Rings Z ¹ and Z ² may be the same or different rings, and may usually be the same ring.

The non-reactive group is not particularly limited, for example, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s- butyl group, C _1-10 alkyl group such as t- butyl group, Preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group, etc., a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, preferably such _{C 5-6} cycloalkyl group), an aryl _{C 6-10} aryl group such as (phenyl group, alkylphenyl group (methylphenyl group (tolyl group), a dimethylphenyl group (xylyl), etc.), preferably C _6-8 aryl group, especially phenyl group, etc., aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, etc.) Hydrocarbon group such as); alkoxy group (such as C _1-4 alkoxy group such as methoxy group); acyl group (such as C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C ₁ such as methoxycarbonyl group) _-4 alkoxycarbonyl group); N, N-disubstituted amino group (for example, N, N-diC _1-6 alkylamino group such as dimethylamino group); halogen atom (fluorine atom, chlorine atom, etc.); Nitro group; cyano group and the like. The alkoxycarbonyl group may be a reactive group depending on the type of reaction (for example, esterification reaction).

Preferred non-reactive groups R ¹ (or R ² ) include alkyl groups (such as C _1-4 alkyl groups), cycloalkyl groups (such as C _5-8 cycloalkyl groups), aryl groups (C _6-10 aryl groups). Etc.), an aralkyl group (such as a C _6-8 aryl-C _1-2 alkyl group), and an alkoxy group (such as a C _1-4 alkoxy group). In particular, an alkyl group (such as a C _1-4 alkyl group), an aryl group (such as a C _6-8 aryl group), and an aralkyl group (such as a C _6-8 aryl-C _1-2 alkyl group).

The groups R ¹ and R ² preferably contain at least a reactive group. Examples of the reactive group include a group containing active hydrogen (an active hydrogen-containing group), a derivative group derived from the active hydrogen-containing group, and the like. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, and an N-monosubstituted amino group [for example, an amino group substituted with a hydrocarbon group (an N-monoC _1-6 alkylamino group such as a methylamino group) )], Carboxyl group, C _1-2 alkoxycarbonyl group, and the like, and are usually a hydroxyl group, an amino group, or an N-monosubstituted amino group (particularly, a hydroxyl group or an amino group).

Examples of the derivative group from the active hydrogen-containing group include a group in which an active hydrogen atom is substituted with a detachable group. Such a group is not particularly limited, but is a group obtained through active hydrogen of a hydroxyl group or an amino group, for example, a group — [X— (R ⁵ O) _n —H] (wherein R ⁵ is alkylene The group X is an oxygen atom (ether group) or an imino group, and n represents 0 or an integer of 1 or more.

Examples of the alkylene group represented by the group R ⁵ include C _2-4 alkylene groups (ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.), and in particular, C _{2− Three} alkylene groups are preferred. In addition, the alkylene group represented by R ⁵ may be the same or different from each other in the corresponding active hydrogen-containing group R ¹ (or R ² ), and is usually the same.

  The substitution number (or addition number) n of the alkyleneoxy unit is the same or different and can be selected from the range of 0 or about 1 to 15, for example, 0 to 12, preferably 0 to 8, more preferably 0 to 6, In particular, it may be 0 or about 1-4. When n is 2 or more, the polyalkoxy group (polyalkyleneoxy group) may be composed of a mixture of the same or different alkylene groups (for example, ethylene group and propylene group). In many cases.

The groups R ¹ and R ² are usually often at least reactive groups. Preferred reactive groups R ¹ and R ² are a hydroxyl group, an amino group, the aforementioned group — [X— (R ⁵ O) _n —H].

The group R ¹ (or R ² ) may be substituted on ring Z ¹ (or ring Z ² ) alone or in combination of two or more. The groups R ¹ and R ² may be the same or different from each other, but are usually the same.

Incidentally, the substitution position of group ^{R 1} (or ^{R 2)} is not particularly limited, for example, when Ring ^{Z 1} and ^{Z 2} is a benzene ring, can be selected from position 2～6- phenyl group. Usually, one reactive group may be substituted at the 3-position and 4-position of the phenyl group. In addition, when rings Z ¹ and Z ² are naphthalene rings, it reacts at any one of positions 5 to 8 (for example, position 5) depending on the substitution position of the naphthyl group (1 or 2-naphthyl group) with respect to fluorene. The sex group is often substituted. In particular, when it is a 2-naphthyl group (β-naphthyl group), a reactive group is often substituted at the 6-position of the naphthyl group, and when it is a 1-naphthyl group (α-naphthyl group). Seems to be often substituted with a reactive group at the 5- or 8-position (particularly the 5-position) of the naphthyl group.

Preferable substitution numbers k1 and k2 are each 1 to 6, preferably 1 to 4, more preferably 1 to 3 (particularly 1 to 2). The number of preferred reactive groups in each group ^R 1, ^{R 2,} 1 to 3, and preferably 1 to 2, more preferably 1. The substitution numbers k1 and k2 may be different but are usually the same in many cases. For example, when k1 and k2 is 1, often both radicals ^{R 1} and ^{R 2} is a reactive group, when k1 and k2 is 2, the two radicals ^{R 1} and two groups ^{R 2} Of these, 1 or 2 groups are often reactive groups (that is, they are often bifunctional or tetrafunctional).

In addition, the groups R ³ and R ⁴ may usually be an alkyl group (C _1-4 alkyl group, particularly a methyl group). The groups R ³ and R ⁴ may be the same or different from one another. In addition, the bonding position (substitution position) of the group R ³ (or R ⁴ ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers m1 and m2 are 0 or 1, in particular 0. The substitution numbers m1 and m2 may be different but are usually the same.

  Representative fluorene compounds include, for example, (1) 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof, (2) 9,9-bis (hydroxynaphthyl) fluorenes or derivatives thereof, (3) 9 , 9-bis (aminophenyl) fluorenes or derivatives thereof.

Specific examples of the fluorene compounds (9,9-bis (hydroxyphenyl) fluorenes) in which the substituents R ¹ and R ² are hydroxyl groups and the ring Z ¹ and ring Z ² are unsubstituted benzene rings include, for example, 9 9,9-bis (monohydroxyphenyl) fluorenes such as 9,9-bis (3-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene; for example, 9,9-bis (3,4) 9,9-bis (dihydroxyphenyl) such as -dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene ) Fluorenes; for example, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bi Examples include 9,9-bis (trihydroxyphenyl) fluorenes such as s (2,4,5-trihydroxyphenyl) fluorene and 9,9-bis (3,4,5-trihydroxyphenyl) fluorene.

Specific examples of the fluorene compounds (9,9-bis (hydroxynaphthyl) fluorenes) in which the groups R ¹ and R ² are hydroxyl groups and the rings Z ¹ and Z ² are naphthalene rings include, for example, 9,9-bis [(5-hydroxynaphth-1-yl)] fluorene 9,9-bis (5-hydroxynaphth-2-yl) fluorene, 9,9-bis (6-hydroxynaphth-1-yl) fluorene, 9,9 9,9-bis (hydroxynaphthyl) fluorenes such as bis (6-hydroxynaphth-2-yl) fluorene; 9,9-bis (polyhydroxynaphthyl) fluorenes corresponding to these monohydroxynaphthylfluorenes ( For example, 9,9-bis (di- or trihydroxynaphthyl) fluorenes) can be exemplified.

Specific examples of the fluorene compounds (9,9-bis (alkyl-hydroxyaryl) fluorenes) in which the substituents R ¹ and R ² include a hydroxyl group and an alkyl group include, for example, biscresol fluorene [9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene, etc.], 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9 9,9-bis (C _1-4 alkyl-hydroxyphenyl) fluorenes such as bis (4-hydroxy-3-butylphenyl) fluorene; bisxylenolfluorene [9,9-bis (4-hydroxy-3,5 -Dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene Emissions, etc.] such as 9,9-bis _{(di-C 1-4} alkyl - hydroxyphenyl) fluorene; 9,9-bis _{(C 1-4} alkyl - dihydroxyphenyl) fluorene; 9,9-bis (di _{C 1- 4-} alkyl-dihydroxyphenyl) fluorene and the like.

Specific examples of the fluorene compounds (9,9-bis (aryl-hydroxyaryl) fluorenes) in which the substituents R ¹ and R ² include a hydroxyl group and an aryl group include, for example, 9,9-bis (3-phenyl- 9,9-bis (C _6-8 aryl-hydroxyphenyl) fluorene such as 4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene; C _6-8 aryl-dihydroxyphenyl) fluorene and the like can be exemplified.

Furthermore, the fluorene compound includes a compound in which a cycloalkyl group, an aralkyl group, an alkoxy group, an acyl group, or the like is substituted in place of the alkyl group or aryl group. Furthermore, specific examples of the fluorene compounds (9,9-bis (aminoaryl) fluorenes) in which the groups R ¹ and R ² are amino groups include, for example, an amino group or N-monosubstituted amino instead of the hydroxyl group. Compound substituted with a group (for example, N—C _1-4 alkylamino group), for example, 9,9-bis (monoaminophenyl) fluorene [9,9-bis (4-aminophenyl) fluorene (bisaniline fluorene) Etc.].

  Derivatives of 9,9-bis (hydroxyaryl) fluorenes include reaction products with haloalkanols and alkylene oxide adducts, for example, the number of moles (n) of alkylene oxide added to the active hydrogen atom, as described above. 1-12, preferably 1-8, more preferably 1-6, especially about 1-4.

In the alkylene oxide adduct, typical compounds in which n is 1 or 2 include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy)- Phenyl] fluorene (bisphenoxyethanol fluorene), 9,9-bis [4- (3-hydroxypropoxy) -phenyl] fluorene and other 9,9-bis (2-hydroxyC _2-4 alkoxy) phenyl] fluorene etc.], Substituted 9,9-bis (hydroxyalkoxyphenyl) fluorene {9,9 such as 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (biscresol ethanolfluorene) - bis (hydroxy _{C 2-4} alkoxy _{-C 1-4} alkylphenyl) Fluorene, 9,9-bis [(2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy - di _{C 1-4} alkyl phenyl) fluorene, 9, 9 bis 9,9-bis such [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene 9 such as _{[(2-hydroxy-C 2-4 alkoxy) -C 6-8} aryl phenyl] fluorene, 9-bis [mono (hydroxyalkoxy) phenyl] fluorenes; 9,9-bis [di or tri (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4- di (2-hydroxyethoxy) phenyl] fluorene such as 9,9-bis [di _{(2-hydroxy-C 2-4} alkoxy) phenyl Fluorene etc.} etc .; corresponding to these compounds, compounds having two alkylene oxide units added to the hydroxyl group {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene 9,9-bis such [2- _{(2-hydroxy-C 2-4 alkoxy) C 2-4} alkoxyphenyl] fluorene such as 9,9-bis {di [2- _{(2-hydroxy-C 2-4} alkoxy) 9,9-bis [mono to tri (hydroxypolyalkoxy) phenyl] fluorene such as 9,9-bis [mono to tri (hydroxydialkoxy) phenyl] fluorenes such as C _2-4 alkoxy] phenyl} fluorene Kind.

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

The fluorene compound can be synthesized by various synthesis methods such as literature [J. Appl. Polym. Sci., 27 (9), 3289, 1982, JP-A-6-145087, JP-A-8-217713, JP 2000-26349 A, JP 2002-47227 A, JP 2003-221352 A], or a method according to these methods. Moreover, the derivative | guide_body of a fluorene compound is a reaction with the addition reaction of the said fluorene compound and alkylene oxide ( _C2-4 alkylene oxide) or alkylene carbonate ( _C2-4 alkylene carbonate), haloalkanol (chloroethanol etc.). It can be prepared by the reaction, the method described in JP-A-11-349657, or a method according to those methods.

  Among the resins using a fluorene compound as a monomer component, examples of the thermoplastic resin having a fluorene skeleton include condensation-type thermoplastic resins such as polyester-based resins (saturated polyester-based resins), polycarbonate-based resins, and polyurethane-based resins. Examples include resins (thermoplastic polyurethane resins), polyamide resins, polyimide resins (thermoplastic polyimide resins), and the like. The thermoplastic resins having a fluorene skeleton may be used alone or in combination of two or more.

  The polyester resin having a fluorene skeleton can be obtained, for example, by polycondensation of a diol component composed of at least the fluorene compound having a hydroxyl group and a dicarboxylic acid component. As the fluorene compound having a hydroxyl group, the alkylene oxide adduct, for example, an alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorenes is often used.

The diol component may be configured by combining a fluorene compound having a hydroxyl group and a diol. Examples of such diols include aliphatic diols [eg, alkylene glycol (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, etc. Or branched C _2-12 alkylene glycol, etc.), (poly) oxy C _2-4 alkylene glycol (eg, diethylene glycol etc.)], alicyclic diol (eg, 1,4-cyclohexanediol, 1,4, etc.) - cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane or an alkylene oxide adduct thereof), aromatic diol (e.g., biphenol, bisphenols such as bisphenol a and their C _2- Alkylene oxide adducts (2,2-bis (4- (such as 2-hydroxyethoxy) phenyl) propane), such as xylylene glycol) and the like. These diols may be used alone or in combination of two or more. Preferred diols are aliphatic such as linear or branched C _2-6 alkylene glycol (eg, linear or branched C _2-4 alkylene glycol such as ethylene glycol and 1,4-butanediol). Diol.

  The ratio of the fluorene compound having a hydroxyl group is, for example, from 15 to 100 mol%, preferably from 30 to 99 mol%, more preferably from 50 to 95 mol% (for example, from 60 to 95 mol%) based on the entire diol component. It may be a degree.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acid components such as saturated C _3-20 aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid (preferably saturated C _3-14 aliphatic dicarboxylic acid); Dicarboxylic acids (C _3-10 cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid), polycyclic alkane dicarboxylic acids (di or tricyclo C _7-10 alkane-dicarboxylic acids such as norbornane dicarboxylic acid), etc. An alicyclic dicarboxylic acid component; arene dicarboxylic acid (for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4′-diphenyldicarboxylic acid, diphenylether-4, 4'-dicarboxylic acid, 4,4'-diphenylmethane dica Aromatic C _8-16 dicarboxylic acids such as rubonic acid and 4,4′-diphenylketone dicarboxylic acid); derivatives capable of forming these esters [for example, acid anhydrides, acid halides (acid chlorides, etc.), lower alkyl esters ( C _1-2 alkyl ester and the like). These dicarboxylic acid components can be used alone or in combination of two or more. For example, the aromatic dicarboxylic acid is mixed with other dicarboxylic acid components (aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid), for example, the former / the latter (molar ratio) = 100/0 to 10/90, preferably 99 / You may use together in the ratio of 1-30 / 70, More preferably about 95 / 5-50 / 50.

  In addition, the diol component may be used in combination with a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc. if necessary, and the dicarboxylic acid component may be trimellitic acid if necessary. Polyvalent carboxylic acids such as pyromellitic acid may be used in combination.

  The number average molecular weight of the polyester-based resin can be selected from a range of about 3000 to 500000, and may be, for example, 5000 to 100000, preferably 8000 to 50000, and more preferably about 10000 to 30000. The terminal group of the polyester resin may be a hydroxyl group and / or a carboxyl group, and may be protected by a protecting group.

  The polyester-based resin can be produced by using a conventional method such as a direct polymerization method (direct esterification method), a transesterification method, an interfacial polymerization method.

  A polyurethane-based resin having a fluorene skeleton can be obtained, for example, by a urethanization reaction between a diol component composed of a fluorene compound having at least a hydroxyl group and a diisocyanate component.

  The diol component may be composed of the hydroxyl group-containing fluorene compound (the compound exemplified in the section of the polyester-based resin such as 9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct) alone. The fluorene compound having a hydroxyl group may be used in combination with the diols exemplified in the section of the polyester resin. Furthermore, as a diol component, a polymer diol component containing a fluorene unit as a structural unit, for example, a polyester diol produced by a reaction between a diol component composed of 9,9-bis (monohydroxyphenyl) fluorenes and a dicarboxylic acid component, A polyether diol produced by the reaction of a diol component composed of 9,9-bis (monohydroxyphenyl) fluorenes and an alkylene oxide can also be used. If necessary, the diol component may be used in combination with a polyol component such as triol. In the diol component, the content of the hydroxyl group-containing fluorene compound is, for example, about 10 to 100 mol%, preferably 20 to 80 mol%, more preferably about 30 to 70 mol%, based on the entire diol component. May be.

  Diisocyanate components include aromatic diisocyanates [tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, toluidine diisocyanate, 1,3-bis (isocyanatophenyl) propane, polymeric MDI, etc.], alicyclic diisocyanates [isophorone diisocyanate, Hydrogenated products of the above aromatic diisocyanates (such as hydrogenated xylylene diisocyanate)], aliphatic diisocyanates [such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate], derivatives thereof (for example, multimers of diisocyanates) And denatured products). These diisocyanate components can be used alone or in combination of two or more.

  In addition, if necessary, the diisocyanate component may be used in combination with polyisocyanates (for example, a triisocyanate compound) or a monoisocyanate compound.

  Polycarbonate resins having a fluorene skeleton include, for example, a diol component composed of a fluorene compound having a hydroxyl group, and a carbonate-forming compound [for example, phosgenes (phosgene, etc.), carbonates (eg, dialkyl carbonates such as dimethyl carbonate). , Carbonic acid diesters such as diaryl carbonate such as diphenyl carbonate, etc.].

  The diol component may be composed of the hydroxyl group-containing fluorene compound (the compound exemplified in the section of the polyester-based resin such as 9,9-bis (monohydroxyphenyl) fluorene and its alkylene oxide adduct) alone. The fluorene compound having a hydroxyl group and a diol may be used.

Examples of the diol include diols exemplified in the polyester-based resin, particularly bisphenols, for example, bis (hydroxyphenyl) alkanes [for example, bis (hydroxyphenyl) such as 2,2-bis (4-hydroxyphenyl) propane. ) C _1-4 alkane etc.], bis (hydroxyphenyl) cycloalkanes [eg bis (hydroxyphenyl) C _5-8 cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclohexane], bis ( Hydroxyphenyl) sulfones [for example, 4,4′-dihydroxydiphenylsulfone and the like], bis (hydroxyphenyl-alkyl) arenes [for example, 4,4 ′-(m-phenylenediisopropylidene) diphenol and the like] and the like. It can be illustrated. These diols may be used alone or in combination of two or more.

  The proportion of the fluorene compound having a hydroxyl group is, for example, from 15 to 100 mol%, preferably from 25 to 80 mol%, more preferably from 30 to 75 mol% (for example, from 35 to 70 mol%), based on the entire diol component. It may be a degree.

  The number average molecular weight of the polycarbonate resin can be selected from a range of, for example, about 3000 to 100,000, and may be, for example, 5,000 to 50,000, preferably 10,000 to 30,000, and more preferably about 12,000 to 25,000. In addition, the terminal of polycarbonate resin may be sealed using monofunctional phenols.

  For example, the polyamide-based resin or the polyimide-based resin having a compound having a fluorene skeleton as a polymerization component includes, for example, at least a part of a polyamine component (diamine component) as a polymerization component by the 9,9-bis (aminophenyl) fluorenes. It can be obtained by configuring.

  Examples of the thermosetting resin include epoxy resins (including phenoxy resins), phenolic resins (such as novolac resins and resol resins), and photocurable resins. In addition, the photocurable resin is a resin (including an oligomer) having a photopolymerizable unsaturated bond such as a (meth) acryloyl group, such as (meth) acrylate, vinyl ester resin, urethane (meth) acrylate, polyester ( Including (meth) acrylate.

Specific examples of the epoxy resin include 9,9-bis (glycidyloxyphenyl) fluorenes in which ring Z ¹ and ring Z ² in the formula (1) are unsubstituted benzene rings, such as 9,9-bis ( 3-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene and the like; 9,9-bis [(2-glycidyloxyethoxy) phenyl] fluorenes such as 9,9-bis [3 -(2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene and the like; 9,9-bis [wherein ring Z ¹ and ring Z ² are naphthalene rings (2-Glycidyloxyethoxy) naphthyl] fluorenes such as 9,9-bis [5- (2-glycidyloxyethoxy) naphth Til] fluorene, 9,9-bis [6- (2-glycidyloxyethoxy) naphthyl] fluorene, 9,9-bis [6- (2-glycidyloxyethoxy) naphth-2-yl] fluorene, etc .; ring Z ¹ and ring ^{Z 2} in the epoxy resin in which an alkyl group is substituted, for example, 9,9-bis [4- (2-glycidyloxyethoxy) -2-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyl Oxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) -3,5-dimethylphenyl] fluorene, etc .; aryl groups were substituted on ring Z ¹ and ring Z ² Epoxy resins such as 9,9-bis [3-phenyl-4- (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5- Diphenyl-4- (2-glycidyloxyethoxy) phenyl] fluorene and the like; polyglycidyl ether type epoxy resin such as 9,9-bis [2,4-bis (2-glycidyloxyethoxy) phenyl] fluorene, 9,9 -Bis [3,4-bis (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-bis (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4 , 5-tris (2-glycidyloxyethoxy) phenyl] fluorene. Examples of the phenoxy resin include epoxy resins having a high degree of polymerization (for example, epoxy resins having a molecular weight of about 1,000 to 100,000 (particularly about 3,000 to 50,000)).

  Phenol resins (novolak-type resins, resol-type resins, etc.) are composed of fluorene compounds having phenolic hydroxyl groups, aldehydes (formaldehyde, etc.) and, if necessary, co-condensation components (for example, phenols, melamines, guanamines, Ureas and the like) can be obtained by reacting in the presence of an acidic catalyst or a basic catalyst.

Among the photocurable resins, typical (meth) acrylates include 9,9-bis ((meth) acryloyloxyphenyl) in which the ring Z ¹ and the ring Z ² in the formula (1) are unsubstituted benzene rings. ) Fluorenes such as 9,9-bis (3- (meth) acryloyloxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, etc .; 9,9-bis [(2- (Meth) acryloyloxyethoxy) phenyl] fluorenes such as 9,9-bis [3- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth)) Acryloyloxyethoxy) phenyl] fluorene and the like; 9,9-bis [(2- (meth) acryloyloxy) wherein ring Z ¹ and ring Z ² are naphthalene rings Ciethoxy) naphthyl] fluorenes such as 9,9-bis [5- (2- (meth) acryloyloxyethoxy) naphthyl] fluorene, 9,9-bis [6- (2- (meth) acryloyloxyethoxy) naphthyl ] Fluorene, 9,9-bis [6- (2- (meth) acryloyloxyethoxy) naphth-2-yl] fluorene, etc .; compounds in which ring Z ¹ and ring Z ² are substituted with alkyl groups, for example, 9,9 -Bis [4- (2- (meth) acryloyloxyethoxy) -2-methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl] fluorene, 9 , 9-bis [4- (2- (meth) acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, etc .; ring Z ¹ and ring Z ² A compound substituted with an aryl group, such as 9,9-bis [3-phenyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-diphenyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like; polyglycidyl ether type compounds such as 9,9-bis [2,4-bis (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9-bis [3,4-bis (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-bis (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9-bis [3,4,5-tris (2- (meth) acryloyloxyethoxy) phenyl] fluorene; in the above formula (1) The induction group - (meth) acrylic acid ester compound ^{R 5} is a propylene group _{^{[X- (R 5 O) n}} -H]; the formula (1), said induction group - [X- ^{(R 5} (Meth) acrylic acid ester of a compound having (O) _n- H] (n is about 2 to 10, preferably about 2 to 5).

  The vinyl ester resin includes a resin in which (meth) acrylic acid is added to the epoxy resin. Urethane (meth) acrylate can be obtained by reaction of a prepolymer having a terminal isocyanate group prepared using an excess amount of polyisocyanate and hydroxyalkyl (meth) acrylate in the production of the polyurethane-based resin. The polyester (meth) acrylate is prepared by preparing a prepolymer having a terminal hydroxyl group or a carboxyl group using an excessive amount of a diol component or a dicarboxylic acid component in the production of the polyester-based resin, and the terminal hydroxyl group of the prepolymer. Alternatively, it can be prepared by esterifying a carboxyl group with a (meth) acrylic monomer ((meth) acrylic acid, hydroxyalkyl (meth) acrylate, etc.).

  Of these photocurable resins, (meth) acrylates and vinyl ester resins having a fluorene skeleton, particularly at least (meth) acrylates are often used.

The photocurable resin is a conventional component such as a photopolymerizable monomer, a photopolymerization initiator (a ketone polymerization initiator such as a benzoin polymerization initiator or a benzophenone polymerization initiator), or a polymerization accelerator. (Tertiary amines, phosphines, etc.), heat stabilizers (hydroquinone dimethyl ether, etc.) and the like may be included. Photopolymerizable monomers include vinyl pyrrolidone, alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butane glycol di (meth) acrylate, hexane glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, etc.], (poly) oxy C _2-4 alkylene [diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, etc.], C _2-4 alkylene oxide of bisphenol A Examples of adducts are di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Kill.

[Metal particle component]
In the present invention, in order to give a high refractive index (and hardness) to the resin composition and to reduce or prevent coloring, a nanometer-sized zirconium oxide component (or zirconium oxide fine particles) is used as a main component as a metal particle component. Such a zirconium oxide component may be prepared by various methods such as a pulverization method and a crystallization method. However, a hydrolytic condensable compound corresponding to zirconium oxide (that is, a hydrolytic condensable zirconium compound) is hydrolyzed. The hydrolyzed condensate obtained (so-called zirconium oxide obtained by the sol-gel method) is preferable. Such a hydrolysis-condensation product can efficiently obtain a nanometer-order zirconium oxide component.

  Examples of the hydrolytic condensable zirconium compound include tetraalkoxyzirconium (for example, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetraisobutoxyzirconium, tetra-n-butoxyzirconium, tetra -S-butoxyzirconium, tetra-t-butoxyzirconium and the like having 1 to 6 carbon atoms, and zirconium alkoxides such as these oligomers.

  The zirconium oxide component may be composed of at least a hydrolytic condensable zirconium compound, and cohydrolysis of the hydrolytic condensable zirconium compound and a hydrolytic condensable metal compound (or hydrolytic condensable organometallic compound) as a cocondensation component. You may comprise a decomposition condensate.

  The metal of the co-condensation component is, for example, a transition metal [for example, a periodic table group 3 metal (for example, yttrium, cerium, etc.), a periodic group 4 metal (for example, titanium, hafnium, etc.), a periodic group 5 metal (for example, , Niobium, tantalum, etc.), Periodic Table Group 6 metals (eg, tungsten), Periodic Table Group 8 metals (eg, iron, etc.)], Periodic Table Group 10 metals (eg, zinc, etc.), Periodic Table It may be a Group 13 metal (eg, aluminum, indium, etc.), a periodic table Group 14 metal (eg, silicon, germanium, tin, etc.), or the like. These co-condensation components may be a single metal compound or a plurality of metal compounds. The co-condensation component (hydrolytic condensable organometallic compound) usually has at least one hydrolytic condensable group (for example, a halogen atom such as an alkoxy group or chlorine atom) directly bonded to a metal atom (for example, titanium). Have.

Typical cocondensation components include, for example, titanium compounds {eg, titanium alkoxides [eg, dialkoxy titanium such as dialkyldialkoxytitanium (dialkyldiC _1-4 alkoxytitanium such as diethyldiethoxytitanium); trialkoxytitanium (Eg, tri-C _1-4 alkoxy titanium such as trimethoxy titanium), alkyl trialkoxy titanium (eg, alkyl tri-C _1-4 alkoxy titanium such as ethyl trimethoxy titanium), aryl trialkoxy titanium (eg, phenyl trimethoxy) Trialkoxy titanium such as aryltri C _1-4 alkoxy titanium such as titanium; tetraalkoxy titanium (eg, tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium) Tan, tetraisobutoxytitanium, tetra-n-butoxytitanium, tetra-C _1-6 alkoxytitanium such as tetra-t-butoxytitanium, etc.), oligomers thereof, etc.}, hydrolytic condensable zinc compounds (eg, dimethoxyethoxyzinc) Zinc alkoxides), hydrolysis-condensable aluminum compounds [e.g. trialkoxyaluminum (trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri-n-butoxyaluminum, tri-s-butoxyaluminum, tri-t- butoxy and tri C _1-4 alkoxy aluminum such as aluminum), aluminum alkoxides such as these oligomers, corresponding to these compounds, metal above exemplified metals (niobium, tungsten, indium And the like, or the like) hydrolysis condensable compounds. These cocondensation components may be used alone or in combination of two or more. In addition, the ratio of a cocondensation component may be 1-60 mol% with respect to the whole hydrolysis-condensable metal compound, Preferably it is 5-55 mol%, More preferably, about 10-50 mol% may be sufficient.

  Note that the zirconium compound and the hydrolytic condensable metal compound as a co-condensation component usually do not have a radical polymerizable group (for example, an unsaturated hydrocarbon group such as a vinyl group or an allyl group, a (meth) acryloyl group, etc.). In many cases, it is a non-radically polymerizable compound.

  The zirconium oxide component produced by such a sol-gel method has a high affinity with the resin due to the alkoxy groups present on the surface, and therefore it is not always necessary to treat the surface. Surface treatment with a carboxylic acid having a functional group, for example, a hydrocarbon group, an acid anhydride, or a silane coupling agent.

  Examples of the carboxylic acid include compounds having an aliphatic hydrocarbon end such as acetic acid and propionic acid, and compounds having an aromatic hydrocarbon end such as benzoic acid. Moreover, the anhydride of these compounds can also be used.

Specific silane coupling agents include, for example, alkoxysilanes [for example, trimethylmethoxysilane, trimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, triethylmethoxysilane, triethyl silane, triphenyl silane, dialkoxy silanes [e.g., dimethyldimethoxysilane, and di C _1-4 alkyl di C _1-4 alkoxysilane such as dimethyl diethoxy silane; for example, methyl phenyl dimethoxy silane, methyl _{C 1-4} alkyl _{-C 6-10} aryl such as phenyl diethoxy silane - di _{C 1-4} alkoxysilane); for example, diphenyldimethoxysilane, diphenyl And di C _6-10 aryldi C _1-4 alkoxysilane such as tetraethoxysilane), etc.], trialkoxysilanes [e.g., methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyl trimethoxy silane, methyltri C _1-4 alkyltri C _1-4 alkoxysilane such as ethoxysilane, ethyltriethoxysilane, etc.); for example, C _6-10 aryltri C _1- such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, etc. ₄ alkoxysilane like; acyl oxy silanes corresponding to these alkoxysilanes [e.g., C _6-10 Arirutori C _1-4 acyloxyalkyl Sila such aryl triacyloxy silane (phenyl triacetoxysilane ), Etc.] and the like. These silane coupling agents may be used alone or in combination of two or more.

  The ratio of the hydrolytic condensable metal compound (for example, hydrolytic condensable zirconium compound) to the carboxylic acid, acid anhydride, and silane coupling agent is the former / the latter in terms of metal atom (for example, zirconium atom) and silicon atom. (Molar ratio) = 1 / 0.1 to 1/2 can be selected, for example, 1 / 0.15 to 1 / 0.9, preferably 1 / 0.2 to 1 / 0.8, more preferably May be about 1 / 0.25 to 1 / 0.7.

  In addition, the hydrolysis condensation (sol-gel reaction) in the case of using a silane coupling agent can be performed using a conventional method, and can usually be performed in a solvent containing at least water. The hydrolysis and condensation may be performed in the presence of a hydrolysis catalyst (for example, an acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, and acetic acid). The produced zirconium oxide component may be either crystalline or amorphous (or amorphous).

  The average diameter of the zirconium oxide component can be selected from the range of nanometer size, for example, 30 nm or less (for example, about 0.1 to 25 nm), particularly 20 nm or less (for example, about 0.2 to 15 nm), and usually 10 nm or less ( For example, it may be about 0.1 to 8 nm), preferably 7 nm or less (for example, about 0.2 to 6 nm), and more preferably 5 nm or less (for example, about 0.3 to 4 nm). Usually, it may be several nm or less (for example, 0.3 to 10 nm, preferably 0.5 to 5 nm, more preferably about 1 to 3 nm).

  In the present invention, it is sufficient that at least a zirconium oxide component is included as the inorganic particle component, and the zirconium oxide component may be combined with other inorganic particle components (inorganic fine particles). As described above, the inorganic particle component is a transition metal such as Group 3 metal, Group 4 metal, Group 5 metal, Group 6 metal, and Group 8 metal of the periodic table, Group 10 metal of the periodic table, and Group 13 metal. , Including inorganic fine particles composed of inorganic metals such as Group 14 metals, metal oxides, hydroxides (aluminum hydroxide, etc.), salts [carbonates (calcium carbonate, etc.), sulfates (magnesium sulfate, calcium sulfate) Etc.), etc., but is usually in the form of an oxide. Examples of the inorganic oxide particle component include periodic group 4 metal oxides (titanium oxide and the like), periodic table group 8 metal oxides (such as iron oxide), and periodic table group 10 metal oxides (for example, Zinc oxide, etc.), Group 13 metal oxides (for example, aluminum oxide, etc.), Periodic table Group 14 metal oxides (for example, silicon oxide, tin oxide, etc.), and the like. These components can be used alone or in combination of two or more. A preferred inorganic particle component is a nanometer-sized inorganic component having a high refractive index, such as titanium oxide.

  Similar to the zirconium oxide component, these inorganic particle components may be prepared by various methods such as a pulverization method and a crystallization method. However, the hydrolytic condensable compound (that is, the hydrolytic condensable inorganic compound) is hydrolyzed. It is preferably a decomposed hydrolysis condensate (an oxide obtained by a so-called sol-gel method). Taking the titanium compound as an example, examples of the hydrolytic condensable compound include alkoxy titanium (for example, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetraisobutoxy titanium, tetra- n-butoxytitanium, tetra-s-butoxytitanium, tetra-t-butoxytitanium and the like having 1 to 6 carbon atoms such as tetraalkoxytitanium), and titaniums such as these oligomers. The inorganic particle component may also be a component produced by cocondensation with a cocondensation component as described above, or may be surface-treated with a surface treatment agent such as a carboxylic acid, an acid anhydride, or a silane coupling agent. Good. Furthermore, the average diameter of the inorganic particle component is the same as that of the zirconium oxide component.

  The inorganic particle component may be a co-condensed particle component of a zirconium oxide component and another inorganic particle component. For example, the inorganic particle component may be a co-condensed particle component obtained by co-condensing a zirconium oxide component and a titanium oxide component at a co-condensation ratio of the co-condensation component or a ratio of the following zirconium oxide component and another inorganic particle component. Good.

  The proportion of the zirconium oxide component in the inorganic particle component (weight% in terms of solid content) is not particularly limited as long as the optical properties are not impaired, and can be selected from a range of about 10 to 100% by weight in terms of solid content. Usually, 30 to 100% by weight (for example 35 to 95% by weight), preferably 40 to 100% by weight (for example 45 to 90% by weight), more preferably 50 to 100% by weight (for example 55 to 80% by weight). ) And is often about 60 to 100% by weight.

  Combining a zirconium oxide component with other inorganic components (particularly nanometer-sized inorganic fine particles) can suppress coloring even if the inorganic component is easily colored (for example, titanium oxide component), and has high transparency and high Refractive index and hardness can be maintained.

  In the resin composition of the present invention, since a resin having a fluorene skeleton and a zirconium oxide component are combined, the zirconium oxide component can be dispersed in the resin while maintaining a nanometer-size particle diameter. Therefore, high transparency can be maintained even when dispersed in the resin, and the refractive index of the resin composition can be improved by utilizing the high refractive index of zirconium oxide. Further, unlike the use of a titanium oxide component alone, a colorless and transparent resin composition without coloring can be obtained by using a zirconium oxide component as a main component.

  In the resin composition of the present invention, the proportion of the zirconium oxide component can be selected depending on the application, and is, for example, 3 to 400 parts by weight (for example, 5 to 350 parts by weight), preferably 100 parts by weight of the resin. May be about 10 to 300 parts by weight, more preferably about 15 to 250 parts by weight (for example, 30 to 250 parts by weight), and usually about 20 to 300 parts by weight.

  In addition, the resin composition of the present invention may be a conventional additive [for example, a stabilizer (such as an antioxidant, an ultraviolet absorber, a light-resistant stabilizer, a heat stabilizer) as long as the transparency does not decrease. , Etc.), plasticizers, colorants, flame retardants, flame retardant aids, plasticizers, impact modifiers, reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents, lubricants, etc.] Good. These additives may be used alone or in combination of two or more.

  The form of the resin composition of the present invention is not particularly limited. For example, (i) a resin composition in which the inorganic particle component is dispersed in the resin, and (ii) a coating composition containing the resin and the inorganic particle component. It may be in the form of The coating composition (ii) may be a solventless coating composition (coating agent) or a coating composition containing a solvent (coating agent). In the present invention, the inorganic particle component is uniformly dispersed while maintaining the nanometer-size particle diameter in the molded body (coating film and the like) formed from the composition.

  In the coating composition (coating liquid), the solvent is not particularly limited, and depending on the type of the resin, a conventional solvent, for example, hydrocarbons (aliphatic hydrocarbons such as hexane, fats such as cyclohexane, etc. Cyclic hydrocarbons, aromatic hydrocarbons such as toluene and xylene), halogenated solvents (such as dichloromethane), alcohols (such as methanol, ethanol, isopropanol), ethers (such as diethyl ether, dioxane, tetrahydrofuran), Examples include esters (such as ethyl acetate), ketones (such as acetone and ethyl methyl ketone), glycol ether esters (such as ethylene glycol monomethyl ether acetate), cellosolves, and carbitols. These solvents may be used alone or in combination of two or more. The ratio of a solvent should just be a range which does not impair applicability | paintability.

  The shape of the molded product of the present invention can be selected according to the application, for example, rod-like or fiber-like, plate-like, film or sheet-like, lens-like (concave lens-like or convex lens-like), prism-like, etc. It may be an original three-dimensional shape. The average thickness of the film (film-like molded product) may be, for example, from 0.01 to 100 μm, preferably from 0.05 to 50 μm, more preferably from about 0.1 to 30 μm, depending on the application.

  The resin composition (and its molded product) of the present invention is excellent in transparency and has a high refractive index. The haze of the composition of the present invention (or a molded product thereof) is 10% or less (for example, 0 to 10%), preferably 5% or less (for example, 0 to 5%), more preferably 1% or less (for example, 0). About 1%). The refractive index of the composition of the present invention (or a molded product thereof) is, for example, 1.63 to 1.85 (for example, 1.64 to 1.80), preferably 1.63 to 1.77 (for example, 1.65 to 1.75), more preferably 1.63 to 1.75 (for example, 1.66 to 1.72), and may be about 1.63 to 1.70.

  The resin composition can be produced by a method of mixing or melt-mixing (or kneading) a resin, an inorganic particle component (an inorganic particle component composed of a zirconium oxide component) and, if necessary, a solvent. A kneader such as an open roller, a kneader, a Banbury mixer, or an extruder can be used for the melt mixing. In addition, the molding is a known molding method such as an injection molding method, injection compression molding method, extrusion molding method, transfer molding method, blow molding method, pressure molding method, coating method (spin coating method, roll coating method, curtain). Coating method, dip coating method, casting molding method, etc.). Moreover, the composition containing a photocurable resin can be molded by irradiating actinic rays (ultraviolet rays, gamma rays, X-rays, etc.) after removing the solvent as necessary.

  The composition of the present invention is composed of a resin and a zirconium oxide component having a nanometer size (average diameter of 30 nm or less) as an inorganic particle component, and usually the zirconium oxide component is uniformly dispersed, so that transparency is impaired. And a molded article having a high refractive index can be obtained efficiently. Furthermore, since the zirconium oxide component is a main component, coloring can be prevented. Moreover, since an inorganic particle component contains a zirconium oxide component, transparency and coloring can be improved while imparting high hardness. Therefore, the resin composition of the present invention can be used for molded articles having various shapes (films or coatings, sheets, lenses, prisms, optical elements such as a light guide plate, etc.).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Preparation of inorganic oxide component]
(Synthesis Example 1: Zirconium oxide component 1)
15.0 g of tetranormal butoxyzirconium was dissolved in 81.4 g of propylene glycol-α-monomethyl ether, and then 94.9 g of a water-propylene glycol-α-monomethyl ether mixed solution in which 1.4 g of water was mixed was stirred. It was dripped. A reaction solution containing 5% by weight of zirconium oxide was prepared by reacting at room temperature for 2 hours with stirring. When the particle size of the composition in the obtained reaction solution was measured by a dynamic scattering method (manufactured by Malvern Instrument Ltd., Zetasizer Nano, Nano-ZS), the average particle size was 2.0 nm. After the solvent was distilled off under reduced pressure from the obtained reaction liquid, it was filtered with a membrane filter (0.5 μm) made of polytetrafluoroethylene (Teflon (registered trademark)) to prepare a 10 wt% solution in terms of zirconium oxide.

(Synthesis Example 2: Zirconium oxide composition 2)
After 15.0 g of tetranormal butoxyzirconium was dissolved in 69.3 g of propylene glycol-α-monomethyl ether, 84.3 g of a water-propylene glycol-α-monomethyl ether mixed solution in which 1.9 g of water was mixed was stirred. It was dripped. After stirring at room temperature for 2 hours, 8.8 g of benzoic anhydride was added, heated at 80 ° C. for 1 hour and reacted to prepare a reaction solution containing 5% by weight of zirconium oxide. When the particle size of the composition was measured by a dynamic scattering method, the average particle size was 2.7 nm. After the solvent was distilled off under reduced pressure from the obtained reaction liquid, it was filtered with a membrane filter (0.5 μm) made of polytetrafluoroethylene (Teflon (registered trademark)) to prepare a 10 wt% solution in terms of zirconium oxide.

(Synthesis example 3: Titanium oxide composition)
After dissolving 15.0 g of tetraisopropoxy titanium in 69.3 g of propylene glycol-α-monomethyl ether, 84.3 g of a water-propylene glycol-α-monomethyl ether mixed solution in which 1.9 g of water is mixed is stirred. It was dripped. After stirring at room temperature for 2 hours, 11.9 g of benzoic anhydride was added, heated at 80 ° C. for 1 hour, and reacted to prepare a reaction solution containing 5% by weight of titanium oxide. When the particle size of the composition was measured by a dynamic scattering method, the average particle size was 2.7 nm. After the solvent was distilled off from the obtained reaction solution under reduced pressure, it was filtered through a membrane filter (0.5 μm) made of polytetrafluoroethylene (Teflon (registered trademark)) to prepare a 10 wt% solution in terms of titanium oxide.

[Preparation of resin composition]
( Reference examples and examples)
A solution obtained in Synthesis Example 1, Synthesis Example 2, and Synthesis Example 3 and an acrylate having a fluorene skeleton (manufactured by Osaka Gas Chemical Co., Ltd., 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene) , “BPEFA”) and pentaerythritol tetraacrylate (hereinafter simply referred to as “PETA”) at a ratio shown in Table 1, and a photopolymerization initiator (manufactured by Nagase Sangyo Co., Ltd.) with respect to 100 parts by weight of the mixture. 2 parts by weight of “Irgacure 184”) was added to prepare a photocurable composition.

(Comparative Examples 1 and 2)
An acrylate having a fluorene skeleton as a resin component (9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene “BPEFA” manufactured by Osaka Gas Chemical Co., Ltd.) (Comparative Example 1) or pentaerythritol tetra 100 parts by weight of acrylate (Comparative Example 2) and 3 parts by weight of a photopolymerization initiator (Irgacure 184) were added to propylene glycol-α-monomethyl ether to prepare a photocurable composition.

(Comparative Examples 3 and 4)
The solution obtained in Synthesis Example 1 (Comparative Example 3) and Synthesis Example 2 (Comparative Example 4) and pentaerythritol tetraacrylate were mixed in the ratio shown in Table 1, and photopolymerization was performed on 100 parts by weight of the mixture. 2 parts by weight of an initiator (Irgacure 184) was added to prepare a photocurable composition.

  The photocurable compositions obtained in the above examples and comparative examples were spin-coated on a glass substrate (Corning, Corning 7059) or a silicon substrate, pre-baked at 90 ° C. for 5 minutes, and then subjected to ultraviolet light (metal halide lamp, wavelength). 354 nm) for 30 seconds to form a transparent cured film.

  The refractive index at a wavelength of 633 nm of the cured film formed on the silicon substrate was measured by a spectral reflection method. Moreover, the haze and pencil hardness were measured using the cured film formed on the glass substrate. Table 1 shows the evaluation results of the composition and properties of the photocurable composition.

From the said table | surface, the refractive index improvement was recognized compared with BPEFA and pentaerythritol tetraacrylate used as a base resin, and the photocurable composition of a reference example and an example was not colored, and pencil hardness also improved. Therefore, it satisfies the characteristics as a hard coat film. The photocuring compositions (Examples 6 to 9) in which Synthesis Example 3 (titanium oxide component) is partially combined have a significantly higher refractive index than the compositions containing only the zirconium oxide component ( Reference Examples 1 to 4). It was confirmed that the presence of the zirconium oxide component was effective without any coloring.

  Thus, by compounding a zirconium oxide component having a particle size of 30 nm or less and a resin having a fluorene skeleton, the refractive index can be easily improved, and coloring that is problematic only by titanium oxide can be suppressed. Further, it can exhibit a pencil hardness higher than that of the base resin, and can be applied to optical materials (such as hard coat films) that require transparency, high refractive index, and hardness.

Claims (6)

A resin composition comprising a base resin having a fluorene skeleton and an inorganic particle component containing a zirconium oxide component and a titanium oxide component having an average diameter of 30 nm or less,
The base resin is 9,9-bis (3- (meth) acryloyloxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, 9,9-bis [3- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [5- (2- (meth) acryloyloxyethoxy) ) Naphtyl] fluorene, 9,9-bis [6- (2- (meth) acryloyloxyethoxy) naphthyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -2-methylphenyl Fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl] fluorene, , 9-bis [4- (2- (meth) acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [3-phenyl-4- (2- (meth) acryloyloxyethoxy) phenyl Fluorene, 9,9-bis [3,5-diphenyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [2,4-bis (2- (meth) acryloyloxy) Ethoxy) phenyl] fluorene, 9,9-bis [3,4-bis (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-bis (2- (meth) acryloyloxy) Ethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tris (2- (meth) acryloyloxyethoxy) phenyl] fluorene and (1)

{ Wherein the rings Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon ring, and R ¹ and R ² are the same or different and are derived from a non-reactive group or an active hydrogen-containing group-[X _{^{- (R 5 O) n -H}} ] ( wherein, ^{R 5} is propylene, X is oxygen atom or imino group, n represents an integer of 1 to 10) indicates, ^{R 3} and ^{R 4} Represents an alkyl group. k1 and k2 are the same or different and represent an integer of 1 or more, and m1 and m2 are the same or different and represent 0 or an integer of 1 to 4}
Is at least one selected from the group consisting of (meth) acrylic acid esters of compounds represented by:
The zirconium oxide component, Ri hydrolyzed condensate der hydrolysis condensable zirconium compound,
The proportion of the zirconium oxide component is 3 to 400 parts by weight with respect to 100 parts by weight of the base resin, and
The ratio is 45 to 90 wt% der Ru resin composition of the zirconium oxide component in the inorganic particle component. The resin composition according to claim 1, wherein the average diameter of the zirconium oxide component is 10 nm or less. The resin composition according to claim 1, wherein the proportion of the zirconium oxide component in the inorganic particle component is 55 to 80 wt%. The resin composition according to claim 1 , wherein the average diameter of the zirconium oxide component is 0.3 to 10 nm , and the ratio of the zirconium oxide component to 100 parts by weight of the base resin is 5 to 350 parts by weight. The molded object formed with the composition in any one of Claims 1 thru | or 4 . The molded article according to claim 5 , wherein the refractive index is 1.6 to 1.85.