KR20150142681A - Wavelength dispersion adjustment agent, resin composition, and method for adjusting wavelength dispersion of resin - Google Patents

Abstract

[식 중, 환 Z는 방향족 탄화수소환, R¹ 및 R²는 치환기, X는 기 -[(OR³)n-Y](식 중, Y는 히드록실기, 머캅토기, 글리시딜옥시기 또는 (메트)아크릴로일옥시기, R³은 알킬렌기, n은 0 이상의 정수를 나타냄) 또는 아미노기, k는 0 내지 4의 정수, m은 0 이상의 정수, p는 1 이상의 정수를 나타냄]
이 첨가제는 수지에 역파장 분산성을 부여(또는 발현)하거나 또는 수지의 파장 분산성을 저감시킬 수 있다.The additive contains a compound having a 9,9-bisarylfluorene skeleton represented by the following formula (1).

Wherein R ¹ and R ² are substituents and X is a group - [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, a glycidyloxy group or a ) Acryloyloxy group, R ³ is an alkylene group and n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is an integer of 1 or more.
This additive can impart (or express) reverse wavelength dispersion to the resin or reduce the wavelength dispersibility of the resin.

Description

WAVELENGTH DISPERSION ADJUSTMENT AGENT, RESIN COMPOSITION, AND METHOD FOR ADJUSTING WAVELENGTH DISPERSION OF RESIN BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wavelength dispersion adjusting agent,

The present invention relates to an additive for imparting (or expressing) an inverse wavelength dispersion property to a resin or for reducing the wavelength dispersibility of the resin, a resin composition containing the additive, and a wavelength dispersion adjusting method for the resin using the additive .

A compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton or the like) is known to have excellent functions such as high refractive index and high heat resistance. Examples of a method for expressing the excellent function of the fluorene skeleton in the resin to enable molding are fluorene compounds having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bisphenoxyethanol fluorene (BPEF), and the like are generally used as constituent components of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

For example, Japanese Patent Application Laid-Open No. 2002-284864 (Patent Document 1) discloses a molding material containing a polyester resin having a 9,9-bisphenylfluorene skeleton. Japanese Patent Application Laid-Open No. 2002-284834 (Patent Document 2) discloses a polyurethane resin having a 9,9-bisphenylfluorene skeleton and crosslinked with a crosslinking agent. In these documents, as a part of the diol component contained in the resin, 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Bisphenoxyethanol fluorene) or the like is used to introduce a fluorene skeleton into the resin.

However, in such a method, a complicated polymerization reaction is required in order to replace the skeleton of the resin with the fluorene skeleton, and thus it can not be applied to a wide range of resins.

In addition, attempts have been made to directly add a fluorene compound to a resin without converting it into a polymer. For example, Japanese Patent Application Laid-Open No. 2005-162785 (Patent Document 3) discloses a resin composition containing a compound having a 9,9-bisphenylfluorene skeleton and a thermoplastic resin. In this document, it is described that a high refractive index or the like can be imparted to a thermoplastic resin by adding a compound having a 9,9-bisphenylfluorene backbone to the thermoplastic resin. In a specific example, 100 weight parts of a polycarbonate resin , 30 to 40 parts by weight of a specific compound (bisphenol fluorene diglycidyl ether, bisphenoxyethanol fluorene or bisphenoxyethanol fluorene diacrylate) was mixed with a transparent film And that the refractive index is increased.

Japanese Patent Laying-Open No. 2011-8017 (Patent Document 4) discloses an optical resin composition containing a transparent resin and a fluorene compound having a 9,9-bisarylfluorene skeleton. It is described in this document that birefringence can be reduced without impairing the mechanical properties and heat resistance of the transparent resin. In a specific example, fluorene-containing polyester resins, 9, Bis (4-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene, or 9,9- Methylphenyl) fluorene, the birefringence of the stretched film was lowered.

Japanese Patent Application Laid-Open No. 2011-21083 (Patent Document 5) discloses that a phenolic compound functions as a nucleating agent (β nucleating agent) for forming a β-crystal structure in a crystalline resin such as polylactic acid have. In this embodiment, 1 to 5% by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is added to poly (L-lactic acid) having an? L-lactic acid in which? -Cells (melting point: 163 占 폚) was formed, and that the Tg changed from 56.5 占 폚 to 60.9 占 폚 to 62.1 占 폚 with the change of the crystal structure.

Japanese Patent Laid-Open Publication No. 2012-211252 (Patent Document 6) discloses a fluorene compound having a 9,9-bisarylfluorene skeleton (such as bisphenoxyethanol fluorene) and a cellulose derivative (such as cellulose triacetate) ≪ / RTI > is disclosed. In this embodiment, it is described that the retardation value of the stretched film containing cellulose triacetate and bisphenoxyethanol fluorene is 0 or a negative value.

On the other hand, the retardation film (retardation film) is an optical member having a function of converting transmitted light into circularly polarized light or elliptically polarized light due to birefringence. These retardation plates are used for color compensation, viewing angle enlargement, reflection prevention, and the like for a display device such as a liquid crystal display device. Examples of materials for the retardation plate include cellulose acetate, polycarbonate resin, cyclic olefin resin and the like .

It is preferable that such a retardation plate has a flat wavelength dispersion characteristic (low wavelength dispersion property), a reverse wavelength dispersion property or a negative wavelength dispersion property (a characteristic in which the retardation (or birefringence) increases as the wavelength increases) There is a case. However, in general, the resin that becomes the material of the above-mentioned retardation plate has a positive wavelength dispersion property (a characteristic in which the retardation (or birefringence) becomes smaller as the wavelength becomes larger).

Among them, Japanese Patent Application Laid-Open No. 2007-213043 (Patent Document 7) discloses a process for producing a dicarboxylic acid component containing an alicyclic dicarboxylic acid component as a main component and a specific bisphenylfluorene compound (bisphenoxyethanol Etc.) and a diol component containing an alicyclic diol compound, and discloses a retardation film having a retardation at a wavelength of 450 to 630 nm that is longer toward the longer wavelength side.

However, in the retardation film of this document, the raw material resin is limited to a specific polyester resin obtained by using a very limited monomer component.

Japanese Patent Application Laid-Open No. 2002-284864 (Claims, Examples) Japanese Patent Application Laid-Open No. 2002-284834 (Claims, Examples) Japanese Patent Application Laid-Open No. 2005-162785 (Claims, Examples) Japanese Patent Application Laid-Open No. 2011-8017 (claims, examples) Japanese Patent Application Laid-Open No. 2011-21083 (claims, examples) Japanese Patent Laid-Open Publication No. 2012-211252 (Claims, Examples) Japanese Patent Application Laid-Open No. 2007-213043 (claims, examples)

It is an object of the present invention to provide an additive (or modifier) capable of imparting (or expressing) an inverse wavelength dispersion (negative wavelength dispersion) to a resin or reducing the wavelength dispersion of the resin and a resin And a method for adjusting the wavelength dispersion of the resin using the above additives.

As described above, a number of techniques for adding a compound having a fluorene skeleton to a resin have been reported. However, by adding a compound having a fluorene skeleton to a resin, it is possible to improve the refractive index, reduce birefringence, Change, and plasticizer effects, and it is not yet fully developed. Also, in Patent Document 7, even when a diol having a fluorene skeleton is used as described in Comparative Examples of this document, a polyester resin with an inverse wavelength dispersion can not be obtained, and among the polyester resins The available monomers are very limited.

Among them, the present inventors have made intensive investigations in order to solve the above problems, and as a result, they have found that a compound having a 9,9-bisarylfluorene skeleton to a resin can unexpectedly impart (or express) reverse wavelength dispersion to the resin, It has a function of adjusting the wavelength dispersion that the wavelength dispersibility of the resin can be reduced and that these compounds have excellent affinity for a wide range of resins and can easily adjust the wavelength dispersibility for a wide range of resins And completed the present invention.

That is, the additive of the present invention is an additive for imparting (or expressing) an inverse wavelength dispersion property (or a negative wavelength dispersion property) to a resin, or reducing the wavelength dispersion property of the resin, and a 9,9-bisarylfluorene skeleton (An inverse wavelength dispersing agent, an inverse wavelength dispersing agent, an inverse wavelength dispersing agent, a wavelength dispersing agent, and a wavelength dispersing agent). Specifically, the additive of the present invention is an additive for bringing the wavelength dispersion property of the resin closer to the reverse wavelength dispersion property (or negative wavelength dispersion property) or to reduce the wavelength dispersion property of the resin. For example, Can be used as an additive for imparting (or expressing) dispersibility (negative wavelength dispersibility) or improving the reverse wavelength dispersion of the resin.

The compound having a 9,9-bisarylfluorene skeleton may be, for example, a compound represented by the following formula (1).

Wherein R ¹ and R ² are substituents and X is a group - [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, a glycidyloxy group or a ) Acryloyloxy group, R ³ is an alkylene group and n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is an integer of 1 or more.

In particular, the compound having a 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (1A).

(Wherein Z, R ¹ , R ² , k, m, R ³ , n and p are as defined in the formula (1)

In the formula (1) or (1A), the ring Z may be a benzene ring or a naphthalene ring, R ¹ may be an alkyl group, k may be 0 to 1, and R ² may be an alkyl group, a cycloalkyl group, M may be 0 to 2, R ³ may be a C _{2 -4} alkylene group, n may be 0 to 2, and p may be 1 to 3.

The compound having a 9,9-bisarylfluorene skeleton is typically represented by 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (Dihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) Fluorine, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene and 9,9-bis (hydroxyalkoxynaphthyl) At least one selected species may be used.

The resin may be a thermoplastic resin, and at least one selected from a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin and a cellulose derivative may be used.

The present invention includes a resin composition comprising a resin (in particular, a cyclic olefin resin) and the wavelength dispersion adjusting agent (fluorene compound). The resin composition of the present invention may not contain an epoxy compound. The present invention also includes molded articles formed from the resin composition. Such a molded article may be an optical molded article (such as an optical film (such as a retardation film)). The molded article of the present invention may be a film (film-shaped formed article), and the formed article may be a drawn film.

In the present invention, it is also possible to add (or mix) the wavelength dispersion adjuster (fluorene compound) to the resin to impart (or express) the reverse wavelength dispersion property to the resin or to control the wavelength dispersion Adjustment methods are also included.

In the present specification, "9,9-bis (hydroxyaryl) fluorene" and "9,9-bis (hydroxy (poly) alkoxyaryl) fluorene" Fluorine skeleton "(specifically, positions 2 to 7 of the fluorene)) as long as it has a" hydroxy (arylene) fluorene skeleton "or a" 9,9-bis (hydroxy) Is used to mean a compound having a substituent. As used herein, the term "9,9-bis (hydroxy) (poly) alkoxyaryl) fluorene" refers to 9,9-bis (hydroxyalkoxyaryl) fluorene and 9,9-bis (hydroxypolyalkoxyaryl ) Fluorene. ≪ / RTI >

The additive of the present invention can impart (or express) reverse wavelength dispersion to the resin or reduce the wavelength dispersibility of the resin. Since the additive of the present invention does not need to be used as a polymerization component or the like, the wavelength dispersion property of the resin can be easily adjusted easily. Further, the additive of the present invention can be added or mixed with a high affinity for a wide range of resins. Further, according to the additive of the present invention, resin properties such as high refractive index can be maintained or maintained. Therefore, the additives of the present invention are very useful or practical.

The additive of the present invention can be used as an additive for imparting (or expressing) an inverse wavelength dispersion property (negative wavelength dispersion property) to a resin or an additive for reducing the wavelength dispersion property of a resin (an inverse wavelength dispersing agent, an inverse wavelength dispersing agent, )to be. This additive (wavelength dispersion adjusting agent) contains a compound having a 9,9-bisarylfluorene skeleton (hereinafter also referred to as a fluorene compound).

[Fluorene compound]

The fluorene compound may have a 9,9-bisarylfluorene skeleton, and may be a compound having no reactive group [e.g., 9,9-bisarylfluorene (e.g., 9,9-bisphenylfluorene) A compound in which p is 0 in the below-mentioned formula (1), etc.], but usually has a reactive group.

Examples of the reactive group include a hydroxyl group, a mercapto group, a carboxyl group, an amino group, a (meth) acryloyloxy group, and an epoxy group (for example, glycidyloxy group). The fluorene compound may contain these reactive groups either singly or in combination.

The reactive group may be directly bonded to 9,9-bisarylfluorene or may be bonded through a suitable linking group (e.g., (poly) oxyalkylene group).

Specific examples of the fluorene compound include compounds represented by the following formula (1).

Wherein R ¹ and R ² are substituents and X is a group - [(OR ³ ) nY] (wherein Y represents a hydroxyl group, a mercapto group, a glycidyloxy group or a meth) acryloyloxy group of acrylic, R ³ is an alkylene group, n represents an integer of 0 or more), or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, p represents an integer of 1 or more;

The formula (1) Examples of the aromatic hydrocarbon rings represented by ring Z, C _{8 -20} condensed benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, condensation of 2 cyclic hydrocarbons (e.g., indene, naphthalene-2 cyclic hydrocarbon group, preferably C _{10 -16} second condensation polycyclic hydrocarbon), the condensed tricyclic hydrocarbons (e.g., anthracene, phenanthrene, etc.) the condensation of 2 to 4 cyclic hydrocarbon, etc.], set ring hydrocarbon rings (biphenyl ring, such as , Bi (ter) C _6-10 arene rings such as terphenyl and binaphthyl, and the like. The two rings Z may be the same or different and may be the same ring. Preferable ring Z includes a benzene ring, a naphthalene ring, and a biphenyl ring, and in particular, a benzene ring may be used.

The group R ¹ in the formula (1), for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydrocarbon group [e.g., an alkyl group, an aryl group (a phenyl group, such as C _6-10 An aryl group) and the like], an acyl group (e.g., an alkylcarbonyl group such as methylcarbonyl, ethylcarbonyl, pentylcarbonyl, etc.), and the like. As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, (e.g., C _{1 -8} alkyl group, especially a methyl group such as a C _{1 -4} alkyl) C _{1 -12} alkyl group, such as t- butyl group Can be exemplified. When k is plural (2 to 4), the plural groups R ¹ may be the same or different from each other. The types of the groups R ¹ substituted on different benzene rings may be the same or different. The bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include 2-position, 7-position, 2-position and 7-position of a fluorene ring. The preferred number of substituents (k) is 0 to 1, especially 0. The two substitution numbers (k) may be the same or different.

The substituent R ² is substituted on a ring Z, usually a non-reactive substituent, such as alkyl (e.g., methyl, ethyl, C _1-12 alkyl groups such as propyl group, an isopropyl group, a butyl group, preferably a C _{1 -8} alkyl group and the like), C _{5 -8} cycloalkyl group, such as cycloalkyl groups (cyclohexyl group, etc.), aryl (e.g., phenyl group, tolyl group, xylyl group, naphthyl group of C _{6 -10} aryl groups such as hydrocarbon group and the like), aralkyl group (benzyl group, C _{6 -10} aryl -C _{1 -4} alkyl group such as a phenethyl group and the like); An alkoxy group such as (methoxy group, ethoxy group, etc. C _{1 -8} alkoxy group), cycloalkoxy groups (cyclohexyloxy group, etc. C _5-10 cycloalkyloxy groups, such as), an aryloxy group (phenoxy group C _{6 -10} aryloxy group), an aralkyloxy group (a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group), etc., wherein R represents a hydrocarbon group (the hydrocarbon group Etc.); An alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group), and the like (wherein R is as defined above); An acyl group (e.g., a C _1-6 acyl group such as an acetyl group); An alkoxycarbonyl group (e.g., a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); A nitro group; Cyano; A substituted amino group (e.g., a dialkylamino group such as a dimethylamino group), and the like.

Examples of preferred groups R ^2, hydrocarbon group [e.g., an alkyl group (e.g., C _{1 -6} alkyl group), cycloalkyl groups (e.g., C _{5 -8} cycloalkyl group), an aryl group (e.g., C _{6 -10} aryl group), aralkyl group (for example there may be mentioned C ₆ -C ₁ aryl _{-8 -2} alkyl group like), alkoxy groups (C _{1 -4} alkoxy group and the like). In a further preferred group R ^2, and the like alkyl group [C _{1 -4} alkyl group (particularly methyl group), etc.], an aryl group, e.g., C _{6 -10} aryl group (especially phenyl group), etc.]. When the group R < ² > is an aryl group, the group R < ² > may form the ring-linked hydrocarbon ring together with the ring Z. [

When m is plural (2 or more) in the same ring Z, the types of the groups R < ² > may be the same or different from each other. In addition, in the two rings Z, the groups R < ² > may be the same or different. The number m of substituents can be selected depending on the kind of ring Z and may be, for example, from 0 to 8, preferably from 0 to 4 (for example, from 0 to 3), more preferably from 0 to 2 . In a different ring Z, the number of substituents (m) may be the same or different, and may be generally the same.

Examples of the alkylene group represented by the group R ³ in the above-mentioned group X of the formula (1) include a C _{2 -} alkyl group such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butane diyl group, ₆ alkylene group, preferably a C _{2 -4} alkylene group, more preferably a C _{2 -3} alkylene group. When n is 2 or more, the alkylene group may contain different alkylene groups or may contain the same alkylene group. In addition, in the two aromatic hydrocarbon rings Z, the groups R ³ may be the same or different, and they may be generally the same.

The number (addition mol number) n of oxyalkylene groups (OR ³ ) may be 0 or more (for example, 0 to 20), and may be 0 to 15 (for example, 1 to 12) May be 0 to 10 (e.g., 1 to 6), more preferably 0 to 4 (e.g., 1 to 4), particularly 0 to 2 (e.g., 0 to 1). Further, depending on the kind of the resin, there is a case where a remarkable improvement effect can be obtained when n is 0 or n is 1 or more. Therefore, any one of compounds in which n is 0 and compounds in which n is 1 or more may be selected depending on the type of resin and the like. The number of substituents (n) may be the same or different for different rings Z.

Preferred X is a group - [(OR ³ ) n Y], particularly preferably Y is a hydroxyl group. In the formula (1), the compound wherein Y is a hydroxyl group is represented by the following formula (1A).

(Wherein Z, R ¹ , R ² , k, m, R ³ , n and p are as defined in the formula (1)

The substitution number (p) of the group X may be at least 1 (for example, from 1 to 6), for example, from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2, The substitution number (p) may be the same or different in each ring Z, and is usually the same in many cases.

In the above formula (1) (or (1A)), the substitution position of the group X is not particularly limited and may be substituted at a proper substitution position of the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2- to 6-position of the phenyl group, preferably at the 4-position. In the case where ring Z is a condensed polycyclic hydrocarbon ring, the group X is a hydrocarbon ring other than the hydrocarbon ring bonded at the 9-position of the fluorene (for example, the 5-position or 6-position of the naphthalene ring) in the condensed polycyclic hydrocarbon ring, In many cases.

The specific fluorene compound (or the compound represented by the above formula (1) or (1A)) includes a 9,9-bis (hydroxyaryl) fluorene [or a 9,9-bis (hydroxyaryl) fluorene skeleton (Hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes], 9,9-bis (hydroxy (poly) alkoxyaryl ), Fluorene (or 9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton such as 9,9-bis A compound wherein X is a group - [(OR ³ ) n-OH] in the above formula (1) such as 9-bis (hydroxy (poly) alkoxynaphthyl) fluorene]; These compounds include compounds in which the hydroxyl group is substituted by a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group.

Examples of the 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene (for example, 9,9-bis (4-hydroxyphenyl) , 9,9-bis (alkyl-hydroxyphenyl) fluorene (for example, 9,9-bis (4-hydroxy- , 5-dimethylphenyl) fluorene such as 9,9-bis (mono- or di-C _{1 -4} alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxy-phenyl) fluorene Yes g., 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene 9,9-fluorene, such as bis (mono- or di-C _{6 -10} aryl-hydroxyphenyl) fluorene], 9,9-bis (Polyhydroxyphenyl) fluorene (for example, 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis 9,9-bis (di or trihydroxyphenyl) fluorene] and the like.

Examples of the 9,9-bis (hydroxynaphthyl) fluorenes include compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes described above, in which the phenyl group is substituted with a naphthyl group, 9-bis (hydroxynaphthyl) fluorene (for example, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9- ) Fluorene] and the like.

Examples of the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include 9,9-bis (hydroxyalkoxyphenyl) fluorene {e.g., 9,9-bis [4- - hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene 9,9-bis such as fluorene (C _{2 -4-hydroxy-alkoxyphenyl)} fluorene ), 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis [4- (2- hydroxyethoxy) 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene and the like, such as bis [4- (2-hydroxypropoxy) 9-bis (mono- or di-C _{1 -4} alkyl-hydroxy-C _{2 -4} alkoxyphenyl)} fluorene, 9,9-bis (aryl-hydroxy-alkoxyphenyl) fluorene {e.g., 9,9- 9,9-bis (4-hydroxyphenyl) phenyl] fluorene such as bis [4- (2-hydroxyethoxy) -bis (mono- or di-C _{6 -10} aryl-hydroxyl C _{2 -4} alkoxyphenyl) fluorene} etc. 9,9-bis (hydroxy-alkoxy-phenyl) fluorene acids (the formula (1) in, n is 1 A compound); 9,9-bis (hydroxydialkoxyphenyl) fluorene {e.g., 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} 9,9-bis (hydroxypolyoxyphenyl) fluorenes (compounds wherein n is 2 or more in the formula (1)) such as bis (hydroxy di C _2-4 alkoxyphenyl) do.

Examples of the 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes include the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes and the phenyl group is substituted with a naphthyl group (9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, such as 9,9-bis (hydroxyalkoxynaphthyl) fluorene 9,9-bis (hydroxy C _{2 -4} alkoxynaphthyl) fluorene such as 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] -Bis (hydroxyalkoxynaphthyl) fluorenes, and the like.

Of these fluorene compounds, in particular 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene [e.g., 9,9-bis (mono- or di-C _{1 -4-alkyl-hydroxyphenyl)} fluorene], 9,9-bis (aryl-hydroxy-phenyl) fluorene [e.g., 9,9-bis (mono- or di-C _{6 -10} aryl-hydroxyphenyl) A compound wherein n is 0 in the formula (1A), such as 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene and the like; 9,9-bis (hydroxy-alkoxy-phenyl) fluorene {e.g., 9,9-bis (hydroxy-C _{2 -4} alkoxyphenyl)} fluorene, 9,9-bis (alkyl-hydroxy-alkoxyphenyl) fluorene {e.g., 9,9-bis (mono- or di-C _1-4 alkyl-hydroxy-C _{2 -4} alkoxyphenyl)} fluorene, 9,9-bis (aryl-hydroxy-alkoxyphenyl) fluorene {e.g., 9,9-bis (mono- or di-C _{6 -10} aryl-C _{2 -4-hydroxy-alkoxyphenyl)}} fluorene, 9,9-bis (hydroxy-alkoxy-naphthyl) fluorene {Y g., 9,9-bis (hydroxy-C _{2 -4} alkoxy-naphthyl) fluorene} etc. (for example, of n is greater than or equal to 1 in the formula (1A), for example, 1 to 4, preferably 1 to 2, more Preferably 1). Particularly, 9,9-bis (hydroxyalkoxyphenyl) fluorene such as 9,9-bis (hydroxyethoxyphenyl) fluorene may be used in order to impart reverse wavelength dispersion to the resin.

The fluorene compounds may be used singly or in combination of two or more.

A commercially available product may be used as the fluorene compound, or a product synthesized by a common method may be used.

[Additive and Resin Composition]

As described above, the additive (fluorene compound) of the present invention is an additive for imparting (or expressing) the reverse wavelength dispersion (or improving the reverse wavelength dispersion of the resin) to the resin (the reverse wavelength dispersion imparting agent, (Wavelength dispersion improver) or an additive (wavelength dispersion adjuster) for reducing the wavelength dispersion of the resin.

That is, by adding or mixing the fluorene compound to the resin, it is possible to improve the reverse wavelength dispersion property (or the degree) of the resin and the fluorene compound-containing resin composition by adding the fluorene compound to the resin (resin not containing or not mixing the fluorene compound) (Or about) the dispersibility. Further, by adding or mixing the fluorene compound to the resin, the wavelength dispersion (or degree) of the resin composition containing the resin and the fluorene compound can be improved by adjusting the wavelength dispersion property of the resin (resin having no fluorene compound added or mixed) (Or so).

In addition, the additive of the present invention is often capable of bringing the wavelength dispersion property of the resin closer to the side of reverse wavelength dispersion (negative wavelength dispersion) (wavelength dispersibility of resin is negative direction) in many cases, It is not necessary to set the dispersibility to the reverse wavelength dispersion property (negative wavelength dispersion property) (for example, the wavelength dispersion property of the resin having the positive wavelength dispersion property may be reduced). In addition, for the purpose of further increasing the reverse wavelength dispersion (negative wavelength dispersion), it may be used for a resin having an inverse wavelength dispersibility.

Specifically, the retardation (or the birefringence) at a wavelength of resin A (λ ₀₎ to N _0A, the wavelength (λ ₁₎ of a phase difference in (but shorter wavelength than λ ₀₎ N _1A, the wavelength (λ ₂₎ (where , a phase difference in a long wavelength than λ ₀₎ N _2A, the phase difference between the resin a and flu a phase difference in the fluorene resin composition B wavelength (λ ₀₎ of containing the compound N _0B, the wavelength (λ ₁₎ N _1B, When the phase difference at the wavelength? ₂ is N _2B , at least one of the following formulas is often satisfied.

_{N 1A / N 0A> N 1B} / N 0B

_N2A / _N0A < _N2B / _N0B

The wavelength range is not particularly limited, but may be a visible light region of, for example, 300 to 800 nm (for example, 350 to 770 nm), preferably 400 to 750 nm (for example, 400 to 700 nm).

? ₀ ,? ₁ , and? ₂ can be set to arbitrary values in the above range. For example,? ₀ may be selected at any wavelength in the range of, for example, 500 to 650 nm (e.g., 550 nm, 589 nm, 590 nm, 600 nm, 630 nm, etc.).

In addition, λ _1, for example, and also provide at least in the 300 to 600nm range of any one or two wavelengths (for example, 350nm, 400nm, 450nm, 500nm , 550nm , etc.), λ ₂ is e.g. (For example, 630 nm, 650 nm, 700 nm, 750 nm, and the like) in the range of 550 to 800 nm.

As the resin, a wide variety of resins can be used (or applied), and either a thermoplastic resin or a curable resin (heat or photo-curable resin) may be used.

As the thermoplastic resin, for example, an olefin resin (e.g., a chain olefin resin [such as an ethylene resin (e.g. polyethylene), a propylene resin (e.g., polypropylene), a polymethylpentene, Etc.), halogen-containing vinyl resins (such as polyvinyl chloride and fluorinated resins), vinyl resins (such as polyvinyl alcohol and acrylonitrile resins), acrylic resins (such as polymethyl methacrylate Methacrylic resin), a styrene-based resin (for example, a styrene-based monomer alone or copolymer (polystyrene, styrene-? -Methylstyrene copolymer and the like), a copolymer of a styrene-based monomer and a copolymerizable monomer (Meth) acrylate copolymer (styrene-methyl methacrylate copolymer, etc.), styrene-maleic anhydride copolymer, etc.), polycarbonate resins (e.g., listen, Aromatic polycarbonate resin, etc.), polythiocarbonate resin, polyester resin (e.g., aliphatic polyester resin (polylactic acid and the like), aromatic polyester resin, etc.), polyacetal resin, polyamide resin For example, aliphatic polyamide resins such as polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, and polyamide 6/66; aromatic polyamide resins such as polyamide MXD) Polyphenylene ether resin, polysulfone resin, polyphenylene sulfide resin, polyimide resin, polyether ketone resin, cellulose derivative, thermoplastic elastomer and the like.

The thermoplastic resins may be used alone or in combination of two or more.

The molecular weight of the thermoplastic resin can be selected depending on the type of resin, and can be selected from a range of, for example, a number average molecular weight of 2000 or more (for example, 3000 or more), and a molecular weight of 5000 or more (for example, 8000 to 1000000 ), Preferably 10000 or more (for example, 12000 to 800000), and more preferably 15000 or more (for example, 20000 to 500000). The molecular weight can be measured by a conventional method, for example, gel permeation chromatography (GPC) in terms of polystyrene.

Examples of the curable resin (heat or photocurable resin) include acrylic resin (thermal or photocurable acrylic resin), phenol resin, amino resin (urea resin, melamine resin and the like), furan resin, unsaturated polyester resin, Epoxy resin, thermosetting urethane resin, silicone resin, thermosetting polyimide resin, diallyl phthalate resin, and vinyl ester resin. The curable resins may be used alone or in combination of two or more. The curable resin may contain a curing agent or a curing accelerator depending on the kind thereof.

The resin (thermoplastic resin, curable resin) may be used alone or in combination of two or more.

The resin may be either a crystalline resin or an amorphous resin.

The resin may be a resin having a positive wavelength dispersion property or a resin having a negative wavelength dispersion property (reverse wavelength dispersion property).

The additive of the present invention may be suitably used for a thermoplastic resin.

In particular, the additive of the present invention may be suitably used for a resin having excellent transparency, for example, a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin, or a cellulose derivative.

Hereinafter, these resins will be described in detail.

(Cyclic olefin resin)

The cyclic olefin resin is a resin containing at least a cyclic olefin as a polymerization component.

The cyclic olefin may be a monocyclic olefin or a polycyclic olefin. The cyclic olefin may have a substituent such as a hydrocarbon group (e.g., an alkyl group (e.g., a C _1-10 alkyl group such as a methyl group, preferably a C _1-5 alkyl group), a cycloalkyl group (e.g., hexyl C _{5 -10} cycloalkyl group) such as a group, an aryl group (e.g., C _{6 -10} aryl group), a phenyl group, an alkenyl group (e.g., Pro C _{2 -10} alkenyl groups such as a phenyl group and the like), cycloalkenyl group (e.g., cyclopentenyl group, cyclohexenyl group and the like of C _{5 -10} cycloalkenyl group and the like), alkali dengi (e. g., ethyl Li dengi such as C _{2 -10} alkali dengi, preferably Advantageously _-5 C ₂ alkylidene group, etc.), etc.], the polar group [for example, an alkoxy group (e.g., C _{1 -10} alkoxy group, preferably a C _{1 -6} alkoxy group such as methoxy group), O (For example, a C _{2 -5} alkanoyl group such as an acetyl group and the like), an acyloxy group (for example, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, (E.g., a C _1-10 alkoxy-carbonyl group such as a butoxycarbonyl group), a cycloalkoxycarbonyl group (e.g., a C _{5 -10} cycloalkyl-carbonyl group such as a cyclohexyloxycarbonyl group)], a hydroxyl group, , A halogen atom, a haloalkyl group, a nitro group, a cyano group, an oxo group (= O), a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group)}. The cyclic olefin may be used alone or in combination of two or more to have a substituent.

Specific examples of cyclic olefins include monocyclic olefins (for example, cycloalkenes (e.g., cyclo-C _{3 -10} alkenes such as cyclobutene, cyclopentene, cycloheptene and cyclooctene), cycloalkadienes g., a cycloalkyl C _{3 -10} alkadi such as cyclopentadiene yen), etc.], 2 cyclic olefin {e.g., norbornyl nenryu e.g., norbornene (such as 2-norbornene), Alkyl norbornene (e.g., 5-methyl-2-norbornene, 5,5 or 5,6-dimethyl-2-norbornene, 5-ethylidene-2-norbornene), aryl norbornene (For example, 5-phenyl-2-norbornene), norbornene having a polar group (for example, cyanonorbornene such as 5-cyano-2-norbornene, Norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5,6-dimethoxycarbonyl-2-norbornene, 5-methyl-5-cyclohexylox Acyloxyno such as cicarbonyl-2-norbornene Haloalkenyl norbornenes such as norbornene (alkoxycarbonyl norbornene, cycloalkoxycarbonyl norbornene and the like), 5,6-di (trifluoromethyl) -2-norbornene, (E.g., oxononorbornene such as norbornene), etc.), norbornadiene (for example, norbornadiene (for example, 2,5-norbornadiene), alkylnorbornadiene Methyl-2,5-norbornadiene, 5,6-dimethyl-2,5-norbornadiene, etc.), aryl norbornadiene (5-phenyl- And the like), norbornadiene having a polar group (for example, cyanonorbornadiene such as 5-cyano-2,5-norbornadiene, 5-methoxycarbonyl- Acyloxynorbornadiene (such as alkoxycarbonyl norbornadiene) such as boranadien, haloalkyl norbornadiene such as 5,6-di (trifluoromethyl) -2,5-norbornadiene and the like ; Oxonorobornadiene such as 7-oxo-2-norbornadiene)] , Tricyclic olefins (for example, tricycloalkene [for example, C _{6 -25} tricycloalkene such as dihydrodicyclopentadiene (dihydrodicyclopentadiene and the like)], tricycloalkadiene [for example, (Dicyclopentadiene, methyldicyclopentadiene and the like), tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene, tricyclo [4.4.0.1 ^{2, 5]} undec-3,8-diene, such as C _6-25 tricycloalkyl alkadiene, etc.], etc.}, 4 g., 4-cyclic olefins [e. g. a multi-ring cyclic olefin or more {for example, a tetra-cycloalkene (e.g. For example, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, etc. of C _{8 -30} tetracyclo alkene, etc.), etc.], 5-cyclic olefins [e.g., penta-cyclo alkadiene (e.g. For example, C _{10 -35} pentacycloalkadiene such as tricyclopentadiene)], 6-ring Olefins such as ^{hexacycloalkenes} (for example, C _{12 -40} ^{hexacycloalkenes} such as ^hexacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14 ] -4-heptadecene and the like) Etc.]} and the like, and the like.

The cyclic olefin resin may be a homopolymer or a copolymer of a cyclic olefin (for example, a copolymer of a monocyclic olefin and a polycyclic olefin, a copolymer of a plurality of polycyclic olefins, etc.), a copolymer of a cyclic olefin and a copolymerizable monomer do.

Examples of the copolymerizable monomers include linear olefins such as linear olefins such as alkenes such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, , C _{2 -20} alkenes such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Noncovalent C _{5 -20} such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7- (Meth) acrylic monomers such as methyl (meth) acrylate and ethyl (meth) acrylate; and polymerizable nitrile compounds such as (meth) acrylonitrile, Acrylic acid esters, (meth) acrylic acid, etc.), unsaturated dicarboxylic acids or derivatives thereof (maleic anhydride, etc.). The copolymerizable monomers may be used singly or in combination of two or more.

In the copolymer of the cyclic olefin and the copolymerizable monomer, the ratio of the cyclic olefin to the total amount of the cyclic olefin and the copolymerizable monomer is, for example, 10 mol% or more (for example, 20 mol% or more) May be 30 mol% or more, and more preferably 40 mol% or more.

Preferred cyclic olefin resins include cyclic olefin copolymers (e.g., cyclic olefins (e.g., cyclic olefins containing at least norbornenes) and copolymerizable monomers such as, for example, chain olefins Of C _{2 -6} alkenes)]).

In particular, among the cyclic olefin copolymers, a cyclic olefin copolymer having a polar group, for example, a cyclic olefin having a polar group {e.g., norbornene having a polar group [e.g., acyloxynorbornene (e.g., alkoxycarbonyl groups such as 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene (for example, C _{1 -10} alkoxy group, preferably a C _{1 -4} alkoxy group), a substituted norbornene, etc.), etc.], etc.}, for a cyclic olefin and a copolymerizable monomer [for example, including at least, the olefin chain (e. g., such as ethylene C _{2 -6} alkenyl) At least a copolymerizable monomer] is preferred.

In the cyclic olefin copolymer having a polar group, for example, the proportion of the cyclic olefin having a polar group to the total of the cyclic olefin is 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more do.

The cyclic olefin resin may be used singly or in combination of two or more.

(Methacrylic resin)

As the methacrylic resin (methacrylic resin, methacrylate resin), a resin containing at least a methacrylic acid ester as a polymerization component may, for example, be mentioned. Usually, the methacrylic resin is an alkyl methacrylate (e.g., methacrylic acid alkyl ester (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2- methacrylic acid such as ethyl hexyl C _{1 -20} alkyl, preferably methacrylic acid, C _{1 -12} alkyl, more preferably methacrylic acid, C _{1 -6} alkyl, in particular methacrylic acid C _{1 -4} alkyl), etc.] As a polymerization component. The alkyl methacrylates may be used singly or in combination of two or more.

Specific examples of the methacrylic resin include alkyl methacrylate (particularly, alkyl methacrylate containing at least methyl methacrylate), a copolymer of alkyl methacrylate (particularly methacrylic acid containing at least methyl methacrylate Alkyl) copolymer with a copolymerizable monomer, and the like.

The copolymerizable monomer is not particularly limited as long as copolymerization is possible, and examples thereof include (meth) acrylic monomers (e.g., (meth) acrylic acid, alkyl acrylates (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, of acrylic acid C _{1 -10} alkyl), alicyclic (meth) acrylate [for example, (meth) acrylate, cycloalkyl (meth) acrylic acid C _5-10 cycloalkyl esters such as cyclohexyl; (Meth) acrylates such as decalinyl (meth) acrylate, norbornyl (meth) acrylate, bornyl (meth) acrylate and adamantyl (meth) acrylate] hydroxy alkyl (meth) acrylates [for example, (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy-C _{2 -6} alkyl], a compound [for example, having three or more acryloyloxy group in a (meth) acrylic (Meth) acrylate (e.g., ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate), alkane triol di (meth) acrylate (e.g., trimethylol ethane tri (meth) acrylate, trimethylol propane tri ) Acrylic Ray (Pentaerythritol tetra (meth) acrylate) such as the polyol poly (meth) acrylate, the alkylene oxide polyols (e.g., ethylene oxide, such as a C _{2 -4} alkylene oxide) adduct of poly ( Acrylate, etc.), (meth) acrylonitrile, styrene monomer (styrene etc.), vinyl ester monomer (vinyl acetate etc.), unsaturated carboxylic acid or anhydride thereof (maleic anhydride, maleic acid, fumaric acid Etc.) can be exemplified. The copolymerizable monomers may be used singly or in combination of two or more.

Preferable examples of the methacrylic resin include a resin containing a methyl methacrylate as a polymerization component, for example, a copolymer containing methyl polymethacrylate and methyl methacrylate as a polymerization component [for example, methyl methacrylate and methacrylic acid Alkyl ester copolymer (e.g., methyl methacrylate-C _{2 -8} alkyl ester copolymer of methacrylic acid, etc.)]. Further, the methyl methacrylate in the copolymer of polymerizable components, the ratio of methacrylic acid monomer is methyl overall [of methyl methacrylate and other monomers (methacrylic acid alkyl esters of C _{2 -8,} wherein the copolymerizable monomer, and so on) (For example, about 55 to 99.9% by weight), preferably 60% by weight or more (for example, about 65 to 99% by weight), more preferably 70% For example, about 75 to 95% by weight).

(Aromatic polycarbonate resin)

Examples of the aromatic polycarbonate resin include a resin containing an aromatic diol and a carbonate-forming compound as a polymerization component.

Examples of the aromatic diol include bisphenols, dihydroxyarenes (hydroquinone, resorcinol, etc.) and the like. As the bisphenols, for example, dihydroxy arene [for example, 4,4'-hydroxybiphenyl-di (hydroxy-C _{6 -10} arenes) such as phenyl], bis (hydroxyphenyl) alkanes EXAMPLES (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) propane, 2,2- ) Bis (hydroxyphenyl) C _{1 -10} alkanes such as diphenylmethane Acids, preferably bis (hydroxyphenyl) C _{1 -8} alkanes], bis (hydroxyphenyl group) alkanes [e.g., 2,2-bis (4-hydroxy-3,3'-ratio ) propane, such as bis (hydroxybiphenyl biphenylyl) C _{1 -10} alkanes, preferably bis (hydroxybiphenyl biphenylyl) C _{1 -8} alkanes], bis (hydroxyphenyl) cycloalkane acids [e. For example, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, such as bis (hydroxyphenyl) C _{4 -10} cycloalkane, preferably bis (hydroxyphenyl) C _{5 -8} cycloalkane], bis (hydroxyphenyl) ether (for example, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether etc. ), Bis (hydroxyphenyl) sulfone (for example, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'- Dihydroxy-3,3'-diphenyldiphenylsulfone), bis (hydroxyphenyl) sulfoxides (for example, 4,4'-dihydroxydiphenyl Dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, etc.), bis (hydroxy Phenyl) sulfides (for example, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,4'- 3,3'-diphenyldiphenyl sulfide), bis (hydroxyphenyl-alkyl) arenes [for example, 4,4 '- (o, m or p- phenylenediisopropylidene) di bis such as a phenol (hydroxy phenyl -C _{1 -4} alkyl) C _6-10 arene, and the like, preferably bis (hydroxyphenyl -C _1-4 alkyl) benzene.

Of these aromatic diols, in particular bis (hydroxyphenyl) alkanes [particularly, 2,2-bis (4-hydroxyphenyl) propane bis (hydroxyphenyl) alkane, C _{1 -4],} bis (hydroxyphenyl -Alkyl) arenes [bis (hydroxyphenyl-C _1-4 alkyl) benzene, etc.]. The aromatic diols may be used singly or in combination of two or more kinds.

Examples of the carbonate-forming compound include phosgene (phosgene, diphosgene, triphosgene, etc.), carbonates (for example, dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc. ), And diaryl carbonates (diphenyl carbonate, dinaphthyl carbonate, etc.)] and the like. Of these, phosgene, diphenyl carbonate and the like may be suitably used. The carbonate-forming compounds may be used singly or in combination of two or more.

The aromatic polycarbonate resins may be used alone or in combination of two or more.

(Aromatic polyester resin)

Examples of the aromatic polyester resins include polyalkylene arylate resins, polyarylate resins (for example, aromatic dicarboxylic acids such as terephthalic acid and aromatic diols such as biphenol, bisphenol A and xylylene glycol, Polyalkylene oxide adducts, etc.))], liquid crystalline polyester resins, and the like.

Examples of the polyalkylene arylate resin include polyalkylene terephthalate resins [for example, polyalkylene terephthalate (for example, poly (ethylene terephthalate), poly (propylene terephthalate), poly _{2 -4} alkylene terephthalate), a copolyester having an alkylene terephthalate unit (a polyalkylene terephthalate unit)], a polyalkylene naphthalate resin [for example, a polyalkylene naphthalate (for example, polyethylene Poly (C _{2 -4} alkylene naphthalate such as naphthalate), copolyester having an alkylene naphthalate unit (polyalkylene naphthalate unit)], a polycycloalkanediarylene terephthalate resin [for example, polycycloal (E. G., Polycyclohexanedimethylene terephthalate), cycloalkane dialkylene &lt; RTI ID = 0.0 &gt; Copolyester having a terephthalate unit (polycycloalkanediylterephthalate unit)], and the like.

The copolyester includes, for example, a diol component (for example, an alkane diol (e.g., a C _2-6 alkane diol such as ethylene glycol, propylene glycol, butanediol, hexanediol, etc.), a polyalkanediol (For example, diethylene glycol, di-hexa C _{2 -4} alkanediol such as polytetramethylene glycol and the like), alicyclic diols (for example, 1,4-cyclohexane dimethanol and the like), aromatic diols (For example, a C _{2 -4} alkylene oxide adduct of bisphenols, etc.)], a dicarboxylic acid component {for example, an aliphatic dicarboxylic acid (for example, glutaric acid, adipic acid, _-12 C ₄ alkane dicarboxylic acids) such as, an aromatic dicarboxylic acid [for example, an asymmetric aromatic dicarboxylic acid (e.g., phthalic acid, isophthalic acid, etc.), diphenyl dicarboxylic acid, etc.], etc. }, A hydroxycarboxylic acid component (e.g., hydroxybenzoic acid), and the like. The copolymerizable components may be used alone or in combination of two or more.

In the copolyester, the proportion of the alkylene arylate unit (alkylene terephthalate unit, alkylene or phthalate unit, etc.) may be, for example, not less than 40% by weight, preferably not less than 50% by weight.

The aromatic polyester resin may be crystalline or amorphous.

The aromatic polyester resin may have a straight chain structure or a branched chain structure.

The aromatic polyester resins may be used singly or in combination of two or more.

(Cellulose derivative)

The cellulose derivative is not particularly limited, and various cellulose derivatives such as cellulose ester, cellulose carbamate (e.g., cellulose phenylcarbamate), cellulose ether and the like can be used.

Examples of the cellulose ester include cellulose acetate such as cellulose diacetate (DAC) and cellulose triacetate (TAC); C _{3 -5} cellulose acylate such as cellulose propionate, cellulose butyrate; And cellulose acetate C _3-5 acylates such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB).

Examples of the cellulose ether include alkyl cellulose (for example, C _{1 -4} alkyl cellulose such as methyl cellulose, ethyl cellulose and the like), hydroxyalkyl cellulose (for example, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (E.g., hydroxy C _{2 -4} alkyl cellulose such as HPC), hydroxyalkyl alkyl cellulose (e.g., hydroxy C _{2 -4} alkyl C _{1 -4} alkyl cellulose such as hydroxypropylmethyl cellulose), carboxy (E.g., carboxymethylcellulose (CMC) and the like), alkyl-carboxyalkylcellulose (methylcarboxymethylcellulose and the like)], derivatives thereof (e.g., CMC salts such as carboxymethylcellulose sodium, Etc.] can be exemplified.

Among these cellulose derivatives, cellulose esters and cellulose ethers are preferable, and cellulose esters (cellulose acylates) such as cellulose acetate and cellulose acetate C _{3 -4} acylate are particularly preferable. More specifically, cellulose esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate may be suitably used as the cellulose derivative.

The cellulose derivatives may be used singly or in combination of two or more kinds.

The proportion of the additive (fluorene compound) to be used may be selected in the range of, for example, about 0.1 parts by weight or more (for example, about 0.2 to 200 parts by weight) relative to 100 parts by weight of the resin, preferably 0.3 to 100 parts by weight, May be about 0.5 to 80 parts by weight, more preferably about 1 to 50 parts by weight, and usually 0.5 to 50 parts by weight (for example, 0.5 to 40 parts by weight, preferably 0.7 to 30 parts by weight, 1 to 20 parts by weight, especially 2 to 18 parts by weight, particularly preferably 3 to 15 parts by weight). In particular, the ratio of the additive may be in the range of 5 to 15 parts by weight (particularly, 8 to 13 parts by weight) relative to 100 parts by weight of the resin in view of easiness of imparting reverse wavelength dispersion to the resin.

(Wavelength dispersion adjusting agent) of the present invention varies depending on the kind of the resin. However, in order to obtain a sufficient effect of adjusting the wavelength dispersion even in a small amount, the use ratio of the additive (fluorene compound) (For example, 0.1 to 9 parts by weight), preferably 8 parts by weight or less (for example, 0.2 to 7 parts by weight), more preferably 6 parts by weight or less (for example, 0.3 to 5.5 parts by weight), particularly 5 parts by weight or less (for example, 0.5 to 3 parts by weight).

In addition, the additives of the present invention are excellent in affinity for resins, and in many cases, resin properties can be maintained or improved at a high level even when added in a relatively large proportion. Therefore, the use ratio of the additive is preferably 10 parts by weight or more (for example, 10 to 100 parts by weight), more preferably 15 parts by weight (for example, 10 parts by weight) (For example, 18 to 80 parts by weight), and more preferably 20 parts by weight or more (for example, 25 to 70 parts by weight). In addition, the phase difference of the resin can be largely adjusted by increasing the proportion of the additive.

Thus, a resin (resin composition) having improved reverse wavelength dispersion (or imparted or expressed) and a resin having low wavelength dispersibility can be obtained by the additive (wavelength dispersion adjusting agent) of the present invention. The present invention also includes such a resin composition, that is, a resin composition containing a resin and a wavelength dispersion adjusting agent (fluorene compound).

In addition, the resin composition may further contain additives other than fluorene compounds such as a filler or a reinforcing agent, a colorant (a salt pigment), a conductive agent, a flame retardant, a plasticizer, a lubricant, a stabilizer (an antioxidant Antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low-stressing agents, carbon materials, etc.) may be included. These additives may be used alone or in combination of two or more. The resin composition may not contain an epoxy compound.

The proportion of other additives can be appropriately selected depending on the kind thereof. For example, the ratio of the stabilizer may be 0.001 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the resin.

Further, the resin composition can be obtained by mixing a resin and a fluorene compound (wavelength dispersion regulator) (and, if necessary, other components (other additives, etc.)). The mixing method is not particularly limited, and may be mixed by, for example, melt kneading, or may be mixed by dissolving each component in a solvent.

The present invention also includes a molded body formed from such a resin composition. The shape of the molded body is not particularly limited and can be appropriately selected depending on the application. For example, the shape of the molded body may be a two-dimensional structure (film shape, sheet shape, plate shape or the like), a three- dimensional structure (tubular shape, rod shape, And the like.

In particular, since the resin composition of the present invention is often excellent in optical properties, an optical material or an optical molding (particularly, an optical film, an optical lens, etc.) may be suitably formed.

The molded article can be produced by using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a cast molding method and the like.

In particular, the resin composition of the present invention is often excellent in various optical properties and is useful for forming films (particularly optical films). Therefore, the present invention also includes a film (optical film, etc.) formed of the resin composition.

The thickness of the film can be selected depending on the application in the range of about 1 to 1000 mu m, for example, about 1 to 200 mu m, preferably 5 to 150 mu m, and more preferably about 10 to 120 mu m.

Such a film (optical film and the like) can be produced by forming (or forming) the above resin composition by a conventional film forming method such as a casting method (solvent casting method), a melt extrusion method, a calendering method and the like.

The film may be a stretched film. The stretched film may be either a uniaxially stretched film or a biaxially stretched film.

The stretching magnification may be about 1.05 to 10 times (for example, 1.1 to 5 times) in each direction in the uniaxial or biaxial stretching, and usually about 1.1 to 3 times (for example, about 1.2 to 2.5 times) . Further, in the case of biaxial stretching, it may be an equi-elongation or a partial elongation. In the case of uniaxial stretching, longitudinal stretching or transverse stretching may also be used.

The thickness of the stretched film may be, for example, 1 to 150 占 퐉, preferably 3 to 120 占 퐉, and more preferably 5 to 100 占 퐉.

Such a stretched film can be obtained by subjecting a film (or an unstretched film) after film formation to a stretching treatment. The stretching method is not particularly limited, and in the case of uniaxial stretching, wet stretching or dry stretching may be used. In the case of biaxial stretching, a tenter method (also referred to as a flat method), a tube method, or the like may be used.

Example

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

In the examples, various characteristics were measured as follows.

(Phase difference, wavelength dispersion)

The retardation (retardation) of the film was measured with a high-speed retardation measurement device RE-100 manufactured by Otsuka Denshi Co., Ltd. Further, in evaluating the wavelength dispersibility, retardation values at 400 nm, 589 nm and 700 nm were measured (retardation values at respective wavelengths were N ₄₀₀ , N ₅₈₉ and N ₇₀₀ ).

(Example 1)

100 parts by weight of cellulose triacetate (manufactured by Daicel, LT55, hereinafter referred to as TAC), 10 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., 11 parts by weight of a stabilizer (hindered phenol-based antioxidant (IRGANOX1010, manufactured by BASF Japan Ltd.) and phosphorus antioxidant (SUMILIZER GP, manufactured by Sumitomo Chemical Co., Ltd.) Melt kneaded at a cylinder temperature of 210 to 290 DEG C using an extruder (KZW15 / 30 MG manufactured by Techno Bell) to obtain a resin composition in the form of a pellet. The ratio of the hindered phenol antioxidant was 2000 ppm based on the total amount of TAC and BPEF, and the ratio of the phosphorus antioxidant was 1000 ppm based on the total amount of TAC and BPEF. Further, the resin composition was transparent and uniformly mixed.

The obtained resin composition was melt-pressed (hot-pressed) using a press molding machine to obtain a film (unstretched film).

Then, various characteristics were measured using the obtained film.

In the film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 0.12 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 0.21 nm, the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 0.24 nm and exhibited reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.57, N ₇₀₀ / N ₅₈₉ = 1.14).

(Example 2)

A film (unstretched film) was obtained in the same manner as in Example 1 except that the amount of BPEF was changed from 11 parts by weight to 18 parts by weight in Example 1. The cylinder temperature was set at 210 to 280 ° C.

Then, on the obtained film, the results of the measurement of the phase difference, a phase difference at a wavelength of 400nm ₍₄₀₀ N) is the phase difference at 2.36nm, wavelength 589nm (N ₅₈₉₎ is the phase difference at 3.05nm, wavelength 700nm (N ₇₀₀₎ is 3.22 nm and exhibited reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.77, N ₇₀₀ / N ₅₈₉ = 1.06).

(Example 3)

The film obtained in Example 1 was uniaxially stretched from 40 mm to 80 mm at 185 캜 and 120 mm / min using a film stretching machine (modified product of 11 A9 type, manufactured by Imoto Seisakusho Co., Ltd.) To give a uniaxially stretched film. As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 336.77 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 585.4 nm, the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 647.54 nm (N ₄₀₀ / N ₅₈₉ = 0.58, N ₇₀₀ / N ₅₈₉ = 1.11).

(Example 4)

The film obtained in Example 2 was subjected to uniaxial stretching at 185 ° C and 120 mm / minute from 40 mm to 80 mm using a film stretching machine (modified type 11A9, manufactured by Imoto Seisakusho Co., Ltd.) Fold uniaxially stretched film. As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 76.34 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 90.29 nm, the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 93.78 nm , And reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.85, N ₇₀₀ / N ₅₈₉ = 1.04).

(Example 5)

Except that 100 parts by weight of a cyclic olefin resin (ARTONF4520, manufactured by JSR Corporation) was used instead of 100 parts by weight of TAC in Example 1, and a hindered phenol antioxidant and a phosphorus antioxidant were not used, To obtain a film (unstretched film). The cylinder temperature was set to 150 to 280 ° C.

As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 0.34 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 0.70 nm and the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 0.79 nm and exhibited reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.48, N ₇₀₀ / N ₅₈₉ = 1.13).

(Example 6)

Except that BPEF was changed to 6,6-bis (9-fluorenylidene) -di (2-naphthol) (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BNF) in Example 5 To obtain a film (unstretched film). The cylinder temperature was set at 210 to 280 ° C.

As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 4.70 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 5.08 nm and the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 5.18 nm and exhibited reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.93, N ₇₀₀ / N ₅₈₉ = 1.02).

(Example 7)

Except that BPEF was changed to 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BOPPEF) in Example 5 In the same manner as in Example 2, a film (unstretched film) was obtained. The cylinder temperature was set at 210 to 280 ° C.

As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 4.98 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 6.05 nm and the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 6.32 nm and exhibited reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.82, N ₇₀₀ / N ₅₈₉ = 1.04).

(Reference Example 1)

A film (unstretched film) was obtained in the same manner as in Example 1 except that BPEF was not used in Example 5. The cylinder temperature was set to 150 to 280 ° C.

As a result of measuring the retardation of the obtained film, the retardation (N ₄₀₀ ) at a wavelength of 400 nm was 1.64 nm, the retardation (N ₅₈₉ ) at a wavelength of 589 nm was 1.24 nm and the retardation (N ₇₀₀ ) at a wavelength of 700 nm was 1.14 nm and exhibited positive wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 1.32, N ₇₀₀ / N ₅₈₉ = 0.92).

The additive of the present invention can be used as an additive for imparting or exhibiting reverse wavelength dispersion property to the resin (or bringing the wavelength dispersion property of the resin closer to the negative wavelength dispersion property) or reducing the wavelength dispersion property of the resin. In addition, such an additive can also obtain an effect derived from a fluorene compound, which is very useful.

Therefore, the resin (or the resin composition containing the resin and the additive (fluorene compound)) modified by the additive of the present invention (for example, the wavelength dispersion property is adjusted or decreased in the negative direction) But it has excellent properties such as high refractive index, high heat resistance, high transparency, and excellent moldability (high melt fluidity, etc.).

Such a resin composition is particularly excellent in optical properties in many cases, and thus is useful for constituting (or forming) a molded article (optical molded article) for optical use. Examples of optical molded articles formed (constituted) by the resin composition include optical films and optical lenses.

As the optical film, in addition to a phase film (or a retardation film), a polarizing film (and a polarization element and a polarizing plate protective film contained therein), an orientation film (orientation film), a viewing angle magnification (compensation film) An antireflective film, an antireflection film, an antiglare film, an ITO film, an anisotropic conductive film, an electromagnetic wave shielding film, a brightness enhancement film, a near infrared absorbing film, A shielding (EMI) film, a film for an electrode substrate, a film for a color filter substrate, a barrier film, a color filter layer, a black matrix layer, and an adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film for use in a display of an apparatus. Specific examples of the display member (or display) having the optical film of the present invention include FPD devices such as a PC monitor, a television, a mobile phone, a car navigation system, and a touch panel ) And the like.

Claims (9)

A wavelength dispersion regulator comprising a compound having a 9,9-bisarylfluorene skeleton, which is an additive for imparting an inverse wavelength dispersion property to a resin or reducing a wavelength dispersion property of a resin. The wavelength dispersion adjusting agent according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1).

Wherein R ¹ and R ² are substituents and X is a group - [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, a glycidyloxy group or a ) Acryloyloxy group, R ³ is an alkylene group and n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is an integer of 1 or more. The wavelength dispersion adjusting agent according to claim 1 or 2, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1A).

(Wherein Z, R ¹ , R ² , k, m, R ³ , n and p are as defined in the formula (1) A compound according to Claim 2 or 3, wherein Ring Z is a benzene ring or naphthalene ring, R ¹ is an alkyl group, k is 0 to 1, R ² is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, To 2, R ³ is a C _2-4 alkylene group, n is 0 to 2, and p is 1 to 3. 5. The compound according to any one of claims 1 to 4, wherein the compound having 9,9-bisarylfluorene backbone is 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl- Phenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (di- or trihydroxyphenyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, And bis (hydroxyalkoxynaphthyl) fluorene. The wavelength dispersion adjusting agent according to any one of claims 1 to 5, wherein the resin is a thermoplastic resin. The wavelength dispersion adjusting agent according to any one of claims 1 to 6, wherein the resin is at least one selected from a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin and a cellulose derivative. A cycloolefin resin, and the wavelength dispersion adjusting agent according to any one of claims 1 to 7. A method for adjusting the wavelength dispersion of a resin, which comprises adding the wavelength dispersion adjusting agent according to any one of claims 1 to 7 to a resin to impart an inverse wavelength dispersion property to the resin, or to reduce a wavelength dispersion property of the resin.