JP6717003B2 - Wavelength dispersion adjusting agent, resin composition containing the same, and optical film using the resin composition - Google Patents

Description

The present invention relates to a wavelength dispersion adjusting agent for adjusting wavelength dispersion performance, a resin composition containing the wavelength dispersion adjusting agent, an optical film using the resin composition, and a wavelength dispersion adjusting method for the optical film.

Liquid crystal displays and organic EL displays are widely used for mobile phones, computer monitors, notebook computers, and televisions. Many optical films are used in liquid crystal displays and organic EL displays to improve display characteristics. In particular, the retardation film plays a major role in improving the contrast when viewed from the front or obliquely and compensating for the color tone.

Liquid crystal displays include vertical alignment type (VA-LCD), in-plane alignment type liquid crystal (IPS-LCD), super twisted nematic type liquid crystal (STN-LCD), reflective type liquid crystal display, semi-transmissive type liquid crystal display, etc. There are many methods, and a retardation film that matches the display is required.

Such a retardation film is used in a display device such as a liquid crystal display device for the purpose of color compensation, widening of viewing angle, improvement of contrast ratio, antireflection, etc., and materials of the retardation film include cellulose resin and polycarbonate. Resins, cyclic olefin resins and the like are used.

Such a retardation film generally has a flat wavelength dispersion property (low wavelength dispersion property) or reverse wavelength dispersion property (a property that the phase difference increases as the wavelength increases) from the viewpoint of improving display performance by preventing color shift. It is preferable to have In particular, a retardation film having a reverse wavelength dispersion property (hereinafter, referred to as “reverse wavelength dispersion film”) is required for a circularly polarizing plate which is preferably used for a reflective liquid crystal display device, a touch panel and an organic EL. However, the resin used as the material of the retardation film generally has a forward wavelength dispersibility (a characteristic in which the retardation decreases as the wavelength increases) in many cases.

Further, from the viewpoint of front visibility of images, a retardation film used for these is required to be a retardation film having an in-plane retardation (Re) represented by the following formula (a) of 100 to 300 nm.

Re=(nx−ny)×d (a)
(In the formula, nx represents the refractive index in the slow axis direction in the film plane, ny represents the refractive index in the fast axis direction in the film plane, and d represents the film thickness.)
For example, when a reverse wavelength dispersion film is used for a circularly polarizing plate which is preferably used for an organic EL, it is known that the retardation is preferably about ¼ (about 140 nm) of the measurement wavelength λ (at this time, reverse). It is known that the ratio Re(450)/Re(550) of the phase difference at the measurement wavelength of 450 nm and the phase difference at the measurement wavelength of 550 nm is preferably close to 0.81 as the wavelength dispersibility. 1). Then, in consideration of the thinning of the display device, the reverse wavelength dispersion film used is also required to be thin.

Various retardation films have been developed to meet the above required characteristics.

For example, a polyester resin obtained by reacting a dicarboxylic acid component containing an alicyclic dicarboxylic acid component as a main component with a diol component containing a specific bisphenylfluorene compound (such as bisphenoxyethanol) and an alicyclic diol compound is used. As a retardation film, a retardation film having a larger retardation at wavelengths of 450 to 630 nm on the longer wavelength side has been proposed (for example, see Patent Document 2). However, the retardation film described in Patent Document 2 has a problem that the film thickness is large. In addition, the retardation film of Patent Document 2 has a problem that it has a light yellow coloration.

Further, as a reverse wavelength dispersion film, a retardation film using a resin composition containing a cellulose resin which is a cellulose ether and a fumarate polymer is proposed (for example, refer to Patent Document 3). Although the retardation film described in Patent Document 3 is not colored, a retardation film capable of exhibiting higher reverse wavelength dispersion is required in order to obtain a thinner film.

JP-A-2004-198478 JP, 2007-213043, A WO2013/038684

The present invention has been made in view of the above problems, and an object thereof is to provide a chromatic dispersion adjusting agent that can impart (or exhibit) reverse wavelength dispersion or reduce forward wavelength dispersion without coloring.

The present inventors have made extensive studies to solve the above problems, and a wavelength dispersion adjusting agent containing a specific compound, a resin composition containing the same, and an optical film using the resin composition solves the above problems. The present invention has been completed and the present invention has been completed. That is, the present invention is a wavelength dispersion adjusting agent containing a compound having a phosphazene skeleton, a resin composition containing the same, and an optical film using the resin composition.

Hereinafter, the present invention will be described in detail.

The wavelength dispersion adjusting agent of the present invention is characterized by containing a compound having a phosphazene skeleton and being capable of imparting (or exhibiting) reverse wavelength dispersibility to the resin or reducing forward wavelength dispersibility without coloring. The wavelength dispersion adjusting agent of the present invention is characterized in that when the wavelength dispersion adjusting agent is used in a reverse wavelength dispersion film, the film can be thinned.

In the present invention, the mechanism for imparting (or expressing) reverse wavelength dispersibility or reducing forward wavelength dispersibility specifically indicates that the relationship of the following formula (b) or (c) is established.

R _1A /R _0A >R _1B /R _0B (b)
R _2A /R _0A <R _2B /R _0B (c)
(In the formula, R _0A is a phase difference (or birefringence) at a wavelength λ ₀ of the resin A having positive birefringence, R _1A is a phase difference at a wavelength λ ₁ of A (however, a wavelength shorter than λ ₀ ), R _2A is a phase difference at a wavelength λ ₂ of A (however, a wavelength longer than λ ₀ ), R _0B is a phase difference at a wavelength λ ₀ of a resin composition B containing A and a phosphazene compound, and R _1B is a wavelength λ of B. The phase difference at ₁ and R _2B indicate the phase difference at the wavelength λ ₂ of B.)
Here, the wavelengths λ ₀ , λ ₁ , and λ ₂ are not particularly limited, but are selected as arbitrary values from the visible light range of 300 to 800 nm, preferably 400 to 750 nm, for example.

The compound having a phosphazene skeleton of the present invention (hereinafter referred to as a phosphazene compound) can impart or increase the reverse wavelength dispersibility in a thin film, and thus is preferably contained in the wavelength dispersion adjusting agent in an amount of 50% by weight.

The phosphazene compound of the present invention is not particularly limited as long as it is a compound having a phosphazene skeleton, but since it can impart or increase reverse wavelength dispersion in a thin film, a cyclic phosphazene compound represented by the following general formula (1) A linear phosphazene compound represented by the following general formula (2) is preferable, and cyclic phosphazene in which R ₁ , R ₂ , R ₃ , and R ₄ in the general formula (1) are an aryloxy group, a substituted amino group, or an arylthio group. A compound and/or a linear phosphazene compound in which R ₅ , R ₆ , R ₇ , and R ₈ in the general formula (2) are an aryloxy group, a substituted amino group, or an arylthio group are more preferable. By using these phosphazene compounds, it is possible to impart or increase reverse wavelength dispersion in a thinner film.

(In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkylthio group, an arylthio group, chlorine, bromine, Represents a group selected from iodine, and m and n together represent an integer of 3 to 25.)

(In the formula, R ₅ , R ₆ , R ₇ , and R ₈ are each independently an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an amino group, a substituted amino group, an alkylthio group, an arylthio group, chlorine, bromine, Represents a group selected from iodine, and k and l together represent an integer of 3 to 10000.)
Specific examples of the phosphazene compound represented by the general formula (1) include hexamethylphosphazene, octamethylphosphazene, hexaethylphosphazene, octaethylphosphazene, hexan-propylphosphazene, octan-propylphosphazene, hexaisopropylphosphazene. , Octaisopropylphosphazene, hexa(n,s or t-)butylphosphazene, octa(n,s or t-)butylphosphazene, and other phosphazene compounds represented by the general formula (1); hexaphenyl A phosphazene compound represented by the general formula (1) having an aryl group such as phosphazene, octaphenylphosphazene, hexabiphenylphosphazene, octabiphenylphosphazene, hexanaphthylphosphazene, octanaphthylphosphazene (these aryl groups include an alkyl group and an alkoxy group). Groups, halogen groups, nitro groups, cyano groups, ester groups and the like may be substituted.); Hexaphenoxyphosphazene, octaphenoxyphosphazene, hexabiphenoxyphosphazene, octabiphenoxyphosphazene, hexanaphthoxyphosphazene, octanaphthoxy A phosphazene compound having an aryloxy group such as phosphazene and represented by the general formula (1) (wherein these aryloxy groups are substituted with alkyl groups, alkoxy groups, halogen groups, nitro groups, cyano groups, ester groups, etc.) A phosphazene compound having an amino group such as hexaaminophosphazene and octaaminophosphazene; hexamethylaminophosphazene, octamethylaminophosphazene, hexaethylaminophosphazene, octaethylaminophosphazene, hexan-propylaminophosphazene, octa n-Propylaminophosphazene, hexaisopropylaminophosphazene, octaisopropylaminophosphazene, hexa(n,s or t-)butylaminophosphazene, octa(n,s or t-)butylaminophosphazene, hexaphenylaminophosphazene, octaphenylamino A phosphazene compound represented by the general formula (1) having a substituted amino group such as phosphazene, hexabiphenylaminophosphazene, octabiphenylaminophosphazene, hexanaphthylaminophosphazene, octanaphthylaminophosphazene (wherein these substituted amino groups are alkyl groups; Alkoxy group, halogen group, nit It may be substituted with a group b, a cyano group, an ester group or the like. ); Hexamethylthiophosphazene, octamethylthiophosphazene, hexaethylthiophosphazene, octaethylthiophosphazene, hexan-propylthiophosphazene, octan-propylthiophosphazene, hexaisopropylthiophosphazene, octaisopropylthiophosphazene, hexa(n, s or a phosphazene compound represented by the general formula (1) having an alkylthio group such as t-)butylthiophosphazene and octa(n,s or t-)butylthiophosphazene; hexaphenylthiophosphazene, octaphenylthiophosphazene, hexa A phosphazene compound represented by the general formula (1) having an arylthio group such as biphenylthiophosphazene, octabiphenylthiophosphazene, hexanaphthylthiophosphazene, octanaphthylthiophosphazene (these aryl groups include an alkyl group, an alkoxy group, a halogen group). Groups, nitro groups, cyano groups, ester groups and the like may be substituted.); Phosphazene compounds having chlorine such as hexachlorophosphazene and octachlorophosphazene and represented by the general formula (1); hexabromophosphazene, A phosphazene compound having bromine such as octabromophosphazene and represented by the general formula (1); a phosphazene compound having iodine such as hexaiodophosphazene and octaiodophosphazene and represented by the general formula (1) can be mentioned. .. These specific phosphazene compounds represented by the general formula (1) may be contained in the wavelength dispersion adjusting agent of the present invention alone or in combination of two or more kinds.

Specific examples of the phosphazene compound represented by the general formula (2) include polydimethylphosphazene, polydiethylphosphazene, polydi-n-propylphosphazene, polydiisopropylphosphazene, and polydi(n,s or t-)butylphosphazene. A phosphazene compound having an alkyl group and represented by the general formula (2); an phosphazene compound represented by the general formula (2) having an aryl group such as polydiphenylphosphazene, polydibiphenylphosphazene, and polydinaphthylphosphazene (these) The aryl group may be substituted with an alkyl group, an alkoxy group, a halogen group, a nitro group, a cyano group, an ester group, etc.); An aryloxy group such as polydiphenoxyphosphazene, polydibiphenoxyphosphazene, and polydinaphthoxyphosphazene And a phosphazene compound represented by the general formula (2) (these aryloxy groups may be substituted with an alkyl group, an alkoxy group, a halogen group, a nitro group, a cyano group, an ester group, etc.); A phosphazene compound having an amino group such as polydiaminophosphazene; polydimethylaminophosphazene, polydiethylaminophosphazene, polydi-n-propylaminophosphazene, polydiisopropylaminophosphazene, polydi(n,s or t-)butylaminophosphazene, polydiphenylaminophosphazene , Polydibiphenylaminophosphazene, polydinaphthylaminophosphazene and the like, and a phosphazene compound represented by the general formula (2) (wherein these substituted amino groups are alkyl groups, alkoxy groups, halogen groups, nitro groups, cyano groups) Groups, ester groups, etc. may be substituted); polydimethylthiophosphazene, polydiethylthiophosphazene, polydi-n-propylthiophosphazene, polydiisopropylthiophosphazene, poly(n,s or t-)butylthiophazene, etc. A phosphazene compound represented by the general formula (2), which has an arylthio group such as polydiphenylthiophosphazene, polydibiphenylthiophosphazene, and polydinaphthylthiophosphazene, and is represented by the general formula (1) A phosphazene compound (these aryl groups may be substituted by an alkyl group, an alkoxy group, a halogen group, a nitro group, a cyano group, an ester group, etc.); ) Phosphazenization Compounds; phosphazene compounds having bromine such as polydibromophosphazene and represented by general formula (1); phosphazene compounds having iodine such as polydiiodophosphazene and represented by general formula (1). These specific phosphazene compounds represented by the general formula (2) may be contained in the wavelength dispersion adjusting agent of the present invention alone or in combination of two or more kinds.

The wavelength dispersion adjusting agent of the present invention can be used as a resin composition containing 0.01 to 30% by weight of the wavelength dispersion adjusting agent and 70 to 99.99% by weight of a resin. Then, in the resin composition, the wavelength dispersion performance of the resin is adjusted by the wavelength dispersion adjusting agent.

In the present invention, the usage ratio of the phosphazene compound can be selected, for example, from the range of 0.01 parts by weight or more with respect to 100 parts by weight of the resin, the compatibility with the resin and the moldability, and the reverse wavelength of the resin. From the viewpoint of easily providing dispersibility, 0.1 to 50 parts by weight is preferable, 0.3 to 40 parts by weight is more preferable, and 0.3 to 30 parts by weight is particularly preferable. As the resin contained in the resin composition, There is no particular limitation, but a thermoplastic resin is preferable in terms of moldability.

Examples of the thermoplastic resin include an olefin resin {for example, a chain olefin resin [ethylene resin (for example, polyethylene), propylene resin (for example, polypropylene), polymethylpentene, and the like], a cyclic olefin resin}, and a halogen. Containing vinyl-based resin (polyvinyl chloride, fluororesin, etc.), vinyl-based resin (eg, polyvinyl alcohol, acrylonitrile-based resin), (meth)acrylic resin (eg, (meth)acrylic resin such as polymethylmethacrylate) Styrenic resin [eg homopolymer or copolymer of styrene monomer (polystyrene, styrene-α-methylstyrene copolymer, etc.), copolymer of styrene monomer and copolymerizable monomer] (Styrene-acrylonitrile copolymer (AS resin), styrene-(meth)acrylic acid ester copolymer (styrene-methyl methacrylate copolymer, etc.), styrene-maleic anhydride copolymer, etc.)], cinnamon Acid ester-based resin [for example, cinnamic acid ester-fumarate ester copolymer (ethyl cinnamate-diisopropyl fumarate copolymer, etc.)], fumarate-based resin [for example, fumarate diester copolymer (fumarate Acid diisopropyl, diisopropyl fumarate-di-2-ethylhexyl fumarate copolymer, etc.), fumaric acid monoester-fumarate diester copolymer (diisopropyl fumarate-monoethyl fumarate copolymer etc.)], polycarbonate resin (eg, , Aromatic-aliphatic polycarbonate resin, aromatic polycarbonate resin, etc.), polythiocarbonate resin, polyester resin [for example, aliphatic polyester resin (polylactic acid, etc.), aromatic polyester resin, etc.], polyacetal resin, polyamide Resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, cellulose resins, polyether sulfone resins, polymaleimide resins, thermoplastic elastomers, and the like, Cyclic olefin resin, (meth)acrylic resin, styrene resin, cinnamic acid ester resin, fumaric acid ester resin, polycarbonate resin, polyester resin, cellulose resin, polyphenylene ether resin, polyether sulfone resin Resins, polysulfone resins, and polymaleimide resins are more preferable. The resin composition of the present invention may contain one kind or two or more kinds of these resins.

The molecular weight of the thermoplastic resin can be selected according to the type of resin, but for example, the number average molecular weight can be selected from the range of 2000 or more, and since moldability is good, it is preferably 5000 or more, more preferably 10,000 or more, 15000 or more is particularly preferable. The molecular weight can be measured by a conventional method, for example, gel permeation chromatography (GPC) in terms of polystyrene.

Hereinafter, preferable resins according to the present invention will be described in detail.

In the present invention, the cyclic olefin-based 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. Moreover, since the cyclic olefin is a substituted group, for example, a hydrocarbon group [e.g., an alkyl group (e.g., C _1-10 alkyl group such as methyl group, reduction of a positive phase difference developability is low, preferably C _{1- 5} alkyl groups), cycloalkyl groups (eg C _5-10 cycloalkyl groups such as cyclohexyl groups), aryl groups (eg C _6-10 aryl groups such as phenyl groups), alkenyl groups (eg propenyl groups etc.) C _2-10 alkenyl group, etc., cycloalkenyl group (eg, C _5-10 cycloalkenyl group such as cyclopentynyl group, cyclohexenyl group, etc.), alkylidene group (eg, C _2-10 alkylidene group such as ethylidene group) , Preferably a C _2-5 alkylidene group or the like) because of less reduction in positive retardation expression], a polar group [eg, an alkoxy group (eg, a C _1-10 alkoxy group such as a methoxy group, a positive position Since the decrease in the phase difference expression is small, it is preferably a C _1-6 alkoxy group), an acyl group (for example, a C _2-5 alkanoyl group such as acetyl group), an acyloxy group [for example, an alkoxycarbonyl group (for example, methoxycarbonyl group). Group, ethoxycarbonyl group, butoxycarbonyl group and other C _1-10 alkoxy-carbonyl groups), cycloalkoxycarbonyl group (eg, cyclohexyloxycarbonyl group and other C _5-10 cycloalkyl-carbonyl groups)], hydroxyl group, Carboxyl group, amino group, substituted amino group, halogen atom, haloalkyl group, nitro group, cyano group, oxo group (=0), heterocyclic group (nitrogen atom-containing heterocyclic group such as pyridyl group), etc.} May be. The cyclic olefin may have a substituent alone or in combination of two or more kinds.

Specific cyclic olefins include monocyclic olefins [for example, cycloalkene (for example, cycloC _3-10 alkene such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, etc.), cycloalkadiene (for example, cyclopentadiene, etc. CycloC _3-10 alkadiene), etc.], bicyclic olefins {eg norbornenes [eg norbornene (eg 2-norbornene), alkyl norbornenes (eg 5-methyl-2-norbornene, 5, 5 or 5,6-Dimethyl-2-norbornene, 5-ethylidene-2-norbornene), arylnorbornene (eg, 5-phenyl-2-norbornene), norbornene having a polar group (eg, cyano such as 5-cyano-21-norbornene) Norbornene; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5,6-dimethoxycarbonyl-2-norbornene, 5-methyl-5-cyclohexyloxycarbonyl-2-norbornene, etc. Acyloxynorbornene (alkoxycarbonylnorbornene, cycloalkoxycarbonylnorbornene, etc.); 5,6-di(trifluoromethyl)-2-norbornene and other haloalkylnorbornenes; 7-oxo-2-norbornene and other oxonorbornenes), etc.], norbornadiene [For example, norbornadiene (for example, 2,5-norbornadiene), alkylnorbornadiene (for example, 5-methyl-2,5-norbornadiene, 5,6-dimethyl-2,5-norbornadiene, etc.), arylnorbornadiene (5-phenyl- 2,5-norbornadiene and the like, and norbornadiene having a polar group (for example, cyanonorbornadiene such as 5-cyano-2,5-norbornadiene; acyloxynorbornadiene such as 5-methoxycarbonyl-2,5-norbornadiene (alkoxycarbonylnorbornadiene etc.) Haloalkylnorbornadiene such as 5,6-di(trifluoromethyl)-2,5-norbornadiene; oxonorbornadiene such as 7-oxo-2-norbornadiene), etc.], tricyclic olefin {eg tricycloalkene [eg, C _6-25 tricycloalkene such as dihydrodicyclopentadiene (such as dihydrodicyclopentadiene)], tricycloalkadiene [eg, If, dicyclopentadiene compound (dicyclopentadiene, methyl dicyclopentadiene, etc.), tricyclo [4.4.0.1 ^{2 · 5]} undec-3,7-diene, tricyclo [4.4.0.1 ^{2 · 5} ] Undeca-3,8-diene and other C _6-25 tricycloalkadiene and the like]}, polycyclic olefins having four or more rings {for example, tetracyclic olefins [for example, tetracycloalkenes (for example, tetracyclo[ 4.4.0.1 ^2.5 . 1 ^7·10 ]-3-dodecene, 8-methyltetracyclo[4.4.0.1 ^2.5· . 1 ^7·10 ]-3-dodecene, 8,9-dimethyltetracyclo[4.4.0.1 ^2.5·5 . 1 ^7·10 ]-3-Dodecene and other C _8-30 tetracycloalkenes and the like], pentacyclic olefins [eg, pentacycloalkadiene (eg, tricyclopentadiene, C _{10-35 pentacycloalkadiene,} etc. ) Etc.], a hexacyclic olefin [eg hexacycloalkene (eg hexacyclo[6.6.1.1 ^3· 6.0 ^2·7 7.0 ^9·14 ]-4-heptadecene and other C _12-40 Hexacycloalkene) etc.] and the like} and other polycyclic olefins.

The cyclic olefin-based 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.), It may be a copolymer of a cyclic olefin and a copolymerizable monomer.

Examples of the copolymerizable monomer include chain olefins, polymerizable nitrile compounds, (meth)acrylic monomers, unsaturated dicarboxylic acids or their derivatives (maleic anhydride, etc.) and the like. The copolymerizable monomers may be used alone or in combination of two or more.

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

In the present invention, examples of the (meth)acrylic resin include resins containing at least a (meth)acrylic acid ester as a polymerization component. Usually, the (meth)acrylic resin is an alkyl (meth)acrylate [for example, an alkyl ester of (meth)acrylic acid (for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, It may be a resin having a C _1-20 alkyl (meth)acrylate as a polymerization component, such as butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, etc. The alkyl (meth)acrylate may be used alone or You may combine 2 or more types.

Specific (meth)acrylic resins include homopolymers or copolymers of alkyl (meth)acrylate, copolymers of alkyl (meth)acrylate and a copolymerizable monomer, and the like.

The copolymerizable monomer is not particularly limited as long as it is copolymerizable, and examples thereof include (meth)acrylic monomers {for example, (meth)acrylic acid, alkyl (meth)acrylate, alicyclic (meth)). Acrylate, hydroxyalkyl (meth)acrylate, compound having 3 or more (meth)acryloyloxy groups, polyol poly(meth)acrylate, poly(meth)acrylate of alkylene oxide adduct of polyol, etc.), (meth)acrylonitrile, styrene -Based monomers (styrene, etc.), vinyl ester-based monomers (vinyl acetate, etc.), (meth)acrylamide, unsaturated power rubonic acid or its anhydrides (maleic anhydride, maleic acid, fumaric acid, cinnamic acid, etc.) ), unsaturated rubic acid or esters thereof (maleic acid ester, fumaric acid ester, cinnamic acid ester, etc.) and the like. The copolymerizable monomers may be used alone or in combination of two or more. The (meth)acrylic resins may be used alone or in combination of two or more.

In the present invention, examples of the polystyrene-based resin include a polystyrene-based polymer containing at least a homopolymer of styrene or a styrene derivative or a copolymer with another monomer. Usually, the styrene derivative is not particularly limited, but examples thereof include alkyl-substituted styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, and isopropylstyrene; alkoxy-substituted styrenes such as methoxystyrene, ethoxystyrene, and dimethoxystyrene; and chlorostyrene. , Halogen-substituted styrenes such as dichlorostyrene, fluorostyrene, difluorostyrene, trifluorostyrene, bromostyrene, iodostyrene, nitro-substituted styrenes such as nitrostyrene, cyano-substituted styrenes such as cyanostyrene, and condensed polycyclic aromatics such as vinylnaphthalene. Group hydrocarbon ring-substituted unsaturated ethylene such as ring-substituted unsaturated ethylene, biphenyl and vinyltriphenyl, and α- and β-substituted styrene such as α-methylstyrene and α,β,β-trifluorostyrene. Good. The monomer copolymerizable with the styrene derivative may be, for example, one or more ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethyl hexyl acrylate. , 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, trimethylpropyltriacrylate, styrene, α-methylstyrene, nitrostyrene, Bromostyrene, iodostyrene, cyanostyrene, chlorostyrene, 4-t-butylstyrene, 4-methylstyrene, vinylbiphenyl, vinyltriphenyl, vinyltoluene, chloromethylstyrene, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, Maleic anhydride, tetrafluoroethylene (and other fluoroethylene), glycidyl methacrylate, carbodiimide methacrylate, C ₁ -C ₁₈ alkyl crotonic acid, n-dibutyl maleate, dioctyl maleic acid, allyl methacrylate, diallyl maleate, diallyl. Malonic acid, methoxybutenyl methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, Vinyl acetate, vinyl carbonate ethylene, epoxy butene, 3,4-dihydroxybutene, hydroxyethyl (meth)acrylate, methacrylamide, acrylamide, butylacrylamide, ethylacrylamide, diacetone acrylamide, butadiene, vinyl ester monomer, vinyl (meth)acrylate , Isopropenyl (meth)acrylate, cycloaliphatic epoxy (meth)acrylate, ethylformamide, 4-vinyl-1,3-dioxolan-2-one, 2,2-dimethyl-4vinyl-1,3-dioxolane, 3,4-Di-acetoxy-1-butene, and monovinyl adipate t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylamide, 2-t-methacryl Butylaminoethyl acid salt, N,N-acry Examples thereof include dimethylaminoethyl acetate, N-(2-methacryloyloxy-ethyl)ethylene urea, and methacrylamide-ethyl ethylene urea. The copolymerizable monomers may be used alone or in combination of two or more.

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

In the present invention, the fumaric acid ester-based resin includes at least a homopolymer of a fumaric acid ester or a fumaric acid ester derivative, or a polymer containing a copolymer with another copolymerizable monomer. The fumarate resin contains a fumarate residue unit, and examples of the residue unit include dimethyl fumarate residue, diethyl fumarate residue, di-n-propyl fumarate residue, and fumarate. Acid diisopropyl residue, di-n-butyl fumarate residue, di-s-butyl fumarate residue, di-t-butyl fumarate residue, di-n-pentyl fumarate residue, di-s fumarate -Pentyl residue, di-t-pentyl fumarate residue, di-n-hexyl fumarate residue, di-s-hexyl fumarate residue, di-t-hexyl fumarate residue, di-2 fumarate -Ethylhexyl, dicyclopropyl fumarate residue, dicyclopentyl fumarate residue, dicyclohexyl fumarate residue, monomethyl fumarate residue, monoethyl fumarate residue, mono-n-propyl fumarate residue, monoisopropyl fumarate residue Residue, mono-n-butyl fumarate residue, mono-s-butyl fumarate residue, mono-t-butyl fumarate residue, mono-n-pentyl fumarate residue, mono-s-pentyl fumarate Residue, mono-t-pentyl fumarate residue, mono-n-hexyl fumarate residue, mono-s-hexyl fumarate residue, mono-t-hexyl fumarate residue, mono-2-ethylhexyl fumarate , Monocyclopropyl fumarate residue, monocyclopentyl fumarate residue, monocyclohexyl fumarate residue and the like.

Examples of the residue unit relating to the copolymerizable monomer include a styrene residue such as a styrene residue and an α-methylstyrene residue; an acrylic acid residue; a methyl acrylate residue, an ethyl acrylate residue, Acrylic acid ester residues such as butyl acrylate residues; Methacrylic acid residues; Methyl methacrylate residues, Ethyl methacrylate residues, Methacrylic acid ester residues such as butyl methacrylate residues; Vinyl acetate residues, Vinyl ester residues such as vinyl propionate residues; acrylonitrile residues; methacrylonitrile residues; olefin residues such as ethylene residues and propylene residues, vinylpyrrolidone residues, vinylpyridine residues, cinnamic acid One or more of ester residues, fumaric acid residues, cinnamic acid residues and the like can be mentioned. The copolymerizable monomers may be used alone or in combination of two or more.

The fumaric acid ester resins may be used alone or in combination of two or more.

In the present invention, the cinnamic acid ester-based resin includes at least a homopolymer of a cinnamic acid ester or a cinnamic acid ester derivative or a polymer containing a copolymer with another copolymerizable monomer. The cinnamic acid ester-based resin contains a cinnamic acid ester residue unit, and examples of the residue unit include a methyl cinnamate residue unit, an ethyl cinnamate residue unit, and an isopropyl cinnamate residue. A cinnamic acid ester residue unit in which a benzene ring in a cinnamic acid ester residue unit such as a group unit has no substituent; an aminocinnamic acid ester residue unit, an alkylcinnamic acid ester residue unit, an alkoxycinnamic acid A cinnamic acid ester residue unit in which a benzene ring such as an ester residue unit has an electron-donating substituent; a nitro group, a bromo group, an iodo group, a cyano group, a chloro group, a sulfonic acid group, a carboxylic acid group, a fluoro group, Or a cinnamic acid ester residue unit whose benzene ring has an electron-withdrawing substituent such as a phenyl group-substituted cinnamic acid ester residue unit.

Examples of the residue unit relating to the copolymerizable monomer include a styrene residue such as a styrene residue and an α-methylstyrene residue; an acrylic acid residue; a methyl acrylate residue, an ethyl acrylate residue, Acrylic acid ester residues such as butyl acrylate residues; Methacrylic acid residues; Methyl methacrylate residues, Ethyl methacrylate residues, Methacrylic acid ester residues such as butyl methacrylate residues; Vinyl acetate residues, Vinyl ester residues such as vinyl propionate residues; acrylonitrile residues; methacrylonitrile residues; olefin residues such as ethylene residues and propylene residues, vinylpyrrolidone residues, vinylpyridine residues, fumaric acid esters Examples thereof include one kind or two or more kinds of residue, fumaric acid residue, cinnamic acid residue and the like. The copolymerizable monomers may be used alone or in combination of two or more.

The cinnamic acid ester resins may be used alone or in combination of two or more kinds.

In the present invention, examples of the polycarbonate-based resin include resins having an aliphatic diol and/or an alicyclic diol and/or an aromatic diol and a carbonate-forming compound as polymerization components.

Examples of the aliphatic diol include diethylene glycol, triethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol (molecular weight 150 to 4000) and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more.

Examples of the alicyclic diol include isosorbide, isomannide, isoidet, tetramethylcyclobutanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediols, pentacyclodiols, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Dimethanol, 3,8-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 3,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 4,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 8 - hydroxy-3-hydroxymethyl-tricyclo [5.2.1.0 ^2.6] decane, 9-hydroxy-3-hydroxymethyl-tricyclo [5.2.1.0 ^2.6] decane, 8-hydroxy 4-hydroxymethyl-tricyclo [5.2.1.0 ^2.6] decane, 9-hydroxy-4-hydroxymethyl-tricyclo [5.2.1.0 ^2.6] decane, spiro having an acetal tube Examples thereof include glycol, but are not limited thereto. These acetals may be used alone or in combination of two or more. Among these dihydroxy compounds, isosorbide obtained by dehydration condensation of sorbitol produced from various starches, which are abundant as resources and are easily available, is easy to obtain and produce, optical properties, and moldability. It is preferably used from the viewpoint of.

Examples of the aromatic diol include bisphenols, dihydroxyarene (hydroquinone, resorcinol, etc.) and the like. Examples of the bisphenols include dihydroxyarene [eg, di(hydroxy C _6-10 arene) such as 4,4′-dihydroxybiphenyl], bis(hydroxyphenyl)alkanes [eg, bis(41-hydroxyphenyl)methane. , 1,1-bis(4-hydroxyphenyl)ethane, 1,11-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2 -Bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-) Dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2 -Bis(3-cyclohexyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)diphenylmethane and other bis(hydroxyphenyl)C _1-10 alkanes, preferably bis(hydroxyphenyl)C _1-8 alkanes] , Bis(hydroxyphenylaryl)alkanes [for example, bis(hydroxybiphenylyl)C _1-10 alkanes such as 2,2-bis(4-hydroxy-3,3′-biphenyl)propane, 1,1-bis( 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis (4-Hydroxyphenyl)cyclopentane, bis(hydroxyphenyl)ethers (eg, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, etc.), bis(hydroxyphenyl)sulfone (Eg, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfone), bis(hydroxy) Phenyl) sulfoxides (For example, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, etc.), bis(hydroxyphenyl ) Sulfides (for example, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide), bis (Hydroxyphenyl-alkyl)arenes [eg, bis(hydroxyphenyl-C _1-4 alkyl)C _6-10 arenes such as 4,4′-(o,m or p-phenylenediisopropylidene)diphenol, bis (Hydroxyphenyl-C _1-4 alkyl)benzene], bishydroxyphenylfluorenes (for example, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene , 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-n-propylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropyl) Phenyl)fluorene, 9,9-bis(4-hydroxy-3-n-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-sec-butylphenyl)fluorene, 9,9-bis(4- Hydroxy-3-tert-propylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-biphenyl)fluorene, 9,9-bis( 4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3 -Isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-biphenyl)fluorene, 9,9-bis (4-(2-hydroxyethoxy)-3,5-dimethylphenyl ) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy) ) Phenyl) fluorene and the like.

Examples of the carbonate-forming compound include phosgenes (phosgene, diphosgene, triphosgene, etc.), carbonates [e.g., dialkyl carbonates (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonates (diphenyl carbonate, dinaphthyl carbonate, etc.), and the like. Diesters] and the like. The carbonate-forming compounds may be used alone or in combination of two or more.

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

In the present invention, as the polyester resin, for example, polyalkylene arylate resin, polyarylate resin [for example, aromatic dicarboxylic acid (terephthalic acid, etc.) and aromatic diol (biphenol, bisphenol A, xylylene glycol, alkylene oxides thereof, etc. And the like) and liquid crystalline polyester resins.

Examples of the polyalkylene arylate resin include polyalkylene terephthalate resin [for example, polyalkylene terephthalate (for example, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate) and alkylene terephthalate unit (polyalkylene terephthalate unit). And a polyalkylene naphthalate resin [for example, polyalkylene naphthalate (for example, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate)], alkylene naphthalate unit (polyalkylene naphthalate unit). Having a copolyester, etc.], a polycycloalkanedialkylene terephthalate resin [eg, a polycycloalkanedialkylene terephthalate (eg, polycyclohexanedimethylene terephthalate), a copolyalcohol having a cycloalkanedialkylene terephthalate unit (polycycloalkanedialkylene terephthalate unit) Polyester, etc.] and the like. In the copolyester, examples of the copolymerization component include a diol component [for example, alkanediol (for example, C _2-6 alkanediol such as ethylene glycol, propylene glycol, butanediol, and hexanediol), polyalkanediol (for example, diethylene glycol). , Di- or hexa-C _2-4 alkane diols such as polytetramethylene glycol, alicyclic diols (such as 1,4-cyclohexanedimethanol), aromatic diols (such as C _2-4 alkylene of bisphenols). Oxide adduct etc.)], dicarboxylic acid component (eg, aliphatic dicarboxylic acid (eg, C _4-12 alkanedicarboxylic acid such as glutaric acid, adipic acid, sebacic acid)), aromatic dicarboxylic acid [eg, asymmetric aromatic Dicarboxylic acid (eg, phthalic acid, isophthalic acid, etc.), diphenyldicarboxylic acid, etc.], hydroxycarboxylic acid component (eg, hydroxybenzoic acid, etc.), and the like. The copolymerization components may be used alone or in combination of two or more. In the copolyester, the proportion of alkylene arylate units (alkylene terephthalate units, alkylene naphthalate units, etc.) may be, for example, 40% by weight or more, preferably 50% by weight or more.

The polyester resin may be crystalline or non-crystalline.

The polyester resin may have a linear structure or a branched structure. The polyester-forming compounds may be used alone or in combination of two or more.

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

In the present invention, the cellulose-based resin is not particularly limited, and various cellulose-based resins such as cellulose ester, cellulose carbamate (eg, cellulose phenyl carbamate), cellulose ether, cellulose ether ester and the like can be used.

Examples of the cellulose ester include cellulose acetate such as cellulose diacetate (DAC) and cellulose triacetate (TAC); cellulose C _2-5 acylate such as cellulose propionate and cellulose butyrate; cellulose acetate propionate (CAP), Cellulose acylate such as cellulose acetate C _2-5 acylate such as cellulose acetate butyrate (CAB) can be mentioned.

Examples of the cellulose ether include alkyl cellulose (for example, C _1-4 alkyl cellulose such as methyl cellulose and ethyl cellulose), hydroxyalkyl cellulose (for example, hydroxy C _{1 -,} such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC)). ₄ such as an alkyl cellulose), hydroxyalkyl alkylcelluloses (e.g., hydroxy _{C 1-4} alkyl _{C 1-4} alkyl celluloses such as hydroxypropyl methylcellulose), carboxyalkyl cellulose (carboxymethyl cellulose (CMC), etc.) these derivatives [for example, CMC salts (such as alkali metal salts) such as sodium carboxymethyl cellulose], alkyl-carboxyalkyl celluloses (such as methyl carboxymethyl cellulose), aralkyl celluloses (such as benzyl cellulose and trityl cellulose), cyanoalkyl celluloses ( Cyanethyl cellulose, etc.), aminoalkyl cellulose (aminoethyl cellulose, etc.) and the like.

Among these cellulose-based resins, cellulose ester, cellulose ether, cellulose ether ester and the like are preferable because they can be solution cast with an organic solvent, and particularly, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate. Preferred are cellulose esters such as rate, cellulose ethers such as ethyl cellulose, and cellulose ether esters such as hydroxypropylmethyl cellulose phthalate.

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

The resin composition according to the present invention, if necessary, other additives (additives that are not phosphazene compounds, for example, fillers or reinforcing agents, colorants (dyes and pigments), conductive agents, flame retardants, plasticizers, Lubricants, stabilizers [antioxidants (hindered phenolic antioxidants, phosphorus antioxidants, etc.), ultraviolet absorbers, heat stabilizers, etc.], release agents, antistatic agents, dispersants, flow control agents, Leveling agent, defoaming agent, surface modifier, stress reducing agent, carbon material, etc.} may be contained. These additives may be used alone or in combination of two or more.

Here, the proportions of the other additives can be appropriately selected according to their types. The proportion of the stabilizer added is not particularly limited, but for example, the proportion of the stabilizer may be 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the resin.

The resin composition according to the present invention can be used as a molded body formed of the resin composition.

In the present invention, the molded body can be manufactured by using, for example, an injection molding method, an injection compression molding method, a melt extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, or the like. ..

The shape of such a molded body is not particularly limited and can be appropriately selected depending on the application, and examples thereof include a film shape and a sheet shape. In particular, the resin composition according to the present invention is often excellent in optical properties, and an optical material or an optical molded product (particularly, an optical film or an optical lens) may be preferably formed.

When the resin composition according to the present invention is used as a film such as an optical film, the thickness of the film is, for example, 1 to 200 μm, preferably 3 to 100 μm, more preferably 5 for thinning a product using the film. It is about 60 μm.

The film may be a stretched film. In addition, such a stretched film may be either a uniaxially stretched film or a biaxially stretched film. The stretching ratio may be about 1.05 to 10 times (for example, 1.1 to 5 times) in each direction in uniaxial stretching or biaxial stretching, and is usually 1.1 to 3 times (for example, 1. 2 to 2.5 times). In the case of biaxial stretching, it may be uniform stretching or uneven stretching. Further, in the case of uniaxial stretching, it may be longitudinal stretching, lateral stretching or oblique stretching. The thickness of the stretched film is, for example, 1 to 200 μm, preferably 3 to 100 μm, and more preferably 5 to 60 μm.

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

Such a film can be produced by forming a film (or molding) of the resin composition by a conventional film forming method, for example, a casting method (solvent casting method), a melt extrusion method, a calender method, or the like.

According to the present invention, it is possible to impart (or develop) reverse wavelength dispersibility to a resin or reduce forward wavelength dispersibility without coloring.

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

The various physical properties shown in the examples were measured by the following methods.
<Analysis of synthetic compounds>
The structural analysis of the compound was performed by ¹ H-NMR and ³¹ P-NMR spectrum analysis using a nuclear magnetic resonance analyzer.
<Measurement of number average molecular weight>
Using a gel permeation chromatography (GPC) device (manufactured by Tosoh Corporation, trade name: C0-8011 (equipped with column GMH _HR- H)), using tetrahydrofuran or dimethylformamide as a solvent at 40° C. Then, it was determined as a standard polystyrene conversion value.
<Measurement of phase difference characteristics>
The retardation characteristics of the optical film were measured using a sample tilt type automatic birefringence meter (manufactured by Oji Scientific Instruments, trade name: KOBRA-WR) using light having a wavelength of 589 nm.
<Measurement of wavelength dispersion characteristics>
Using a sample tilt type automatic birefringence meter (manufactured by Oji Scientific Instruments, trade name: KOBRA-WR), optical as a ratio of the phase difference Re(450) due to light with a wavelength of 450 nm and the phase difference Re(550) due to light with a wavelength of 550 nm The wavelength dispersion characteristics of the film were measured.

Synthesis example 1 (hexaphenylthiophosphazene)
To a 300 ml flask equipped with a reflux condenser, thiophenol (131.7 g, 0.97 mol) was added, and THF (tetrahydrofuran) (100 ml) was added and dissolved. Metallic sodium (25.0 g, 108 gram atom) was added to this solution at 50° C. or lower, the temperature was raised to 60° C. over 1 hour after the addition was completed, and then the mixture was stirred at 60° C. to 68° C. for 4 hours to obtain thiol. A THF solution of phenol sodium salt was obtained.

Separately, a 20% chlorobenzene solution (290 g, 0.50 mol) of hexachlorocyclotriphosphazene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a 1 liter flask, and THF of the thiophenol sodium salt prepared above was added to this solution. The solution was slowly added dropwise while maintaining the temperature at 30°C or lower, and after the addition, the mixture was stirred at 30°C or lower for 1 hour, and further heated and stirred under solvent reflux (70°C) for 24 hours.

After completion of the reaction, the reaction solution was filtered and concentrated, and then the concentrated solution was dissolved in chlorobenzene (10 liters). This solution was washed 3 times with a 5% aqueous sodium hydroxide solution, once with 5% hydrochloric acid, neutralized with 7% aqueous sodium hydrogen carbonate, and then washed twice with water. Then, chlorobenzene was distilled off under reduced pressure to obtain hexaphenylthiophosphazene (yield: 83.1%).

Synthesis example 2 (hexanaphthoxyphosphazene)
2-Naphthol (231 g, 1.10 mol) was placed in a 1-liter flask equipped with a Dean Stark trap-equipped reflux condenser and a dropping funnel, chlorobenzene (500 ml) was added, and the mixture was stirred until it became homogeneous to give a solution. .. A 48% aqueous sodium hydroxide solution (83.3 g, 1.00 mol as NaOH) was slowly added dropwise to this solution, and the temperature was raised to 132° C. over 1 hour after completion of the addition. During this time, water in the aqueous sodium hydroxide solution and water produced by the reaction were removed as azeotropes with chlorobenzene from the system by using a Dean Stark trap, and chlorobenzene was returned to the system. Then, the reaction solution was stirred under reflux for 4 hours to sufficiently remove water in the system to obtain a chlorobenzene dispersion liquid of sodium salt of 2-naphthol.

Separately, a 20% chlorobenzene solution of hexachlorocyclotriphosphazene (290 g, 0.50 mol) was placed in a 1-liter flask, and the chlorobenzene dispersion liquid of sodium salt of 2-naphthol prepared above was added to the solution at 30°C. While maintaining the temperature below, the mixture was slowly added dropwise, and after the addition, the mixture was stirred at 30° C. or lower for 1 hour, further heated and then stirred under solvent reflux (132° C.) for 24 hours.

After completion of the reaction, the reaction solution was washed 3 times with a 5% aqueous sodium hydroxide solution, once with 5% hydrochloric acid, neutralized with 7% aqueous sodium hydrogen carbonate, and then washed twice with water. Then, chlorobenzene was distilled off under reduced pressure to obtain hexanaphthoxyphosphazene (yield: 51.2%).

Synthesis example 3 (synthesis of chain phosphazene compound, polydiphenylthiophosphazene)
Hexachlorocyclotriphosphazene was heated at 250° C. for 8 hours under an argon gas atmosphere to obtain polydichlorophosphazene having a weight average molecular weight of about 10,000.

Thiophenol (131.7 g, 097 mol) was added to a 300 ml flask equipped with a reflux condenser, and THF (100 ml) was added and dissolved. Metallic sodium (2.0 g, 1.08 gram atom) was added to this solution at 50° C. or lower, the temperature was raised to 60° C. over 1 hour after the addition was completed, and then the mixture was stirred at 60° C. to 68° C. for 4 hours. A THF solution of thiophenol sodium salt was obtained.

Separately, a solution of 75 g (0.65 mol) of polydichlorophosphazene dissolved in THF (750 ml) was weighed into a 10-liter flask, and the THF solution of thiophenol sodium salt was slowly added while keeping the temperature below 30°C. After dropping, the mixture was stirred at 30° C. or lower for 1 hour, further heated and stirred under solvent reflux (70° C.) for 24 hours.

After completion of the reaction, filtration and concentration are carried out, redissolved in 5 liters of chlorobenzene, washed 3 times with 5% aqueous sodium hydroxide solution and once with 5% hydrochloric acid, neutralized with 7% aqueous sodium hydrogen carbonate and washed with water. I went twice. Then, chlorobenzene was distilled off under reduced pressure to obtain polydiphenylthiophosphazene (yield 70.2%).

Synthesis Example 4 (diisopropyl fumarate/monoisopropyl fumarate copolymer)
28 g of diisopropyl fumarate, 22 g of monoisopropyl fumarate and 0.58 g of tert-butylperoxypivalate, which is a polymerization initiator, were put into a glass ampoule having a volume of 75 mL, and nitrogen substitution and depressurization were repeated, and the mixture was sealed under reduced pressure. .. This ampoule was placed in a constant temperature bath at 46° C. and held for 84 hours for radical polymerization. After the completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 200 g of tetrahydrofuran. This polymer solution was added dropwise to 4 L of hexane for precipitation, followed by vacuum drying at 80° C. for 10 hours to obtain 15 g of diisopropyl fumarate/monoisopropyl fumarate copolymer (yield 30.0% ). The number average molecular weight of the obtained polymer was 23,000, diisopropyl fumarate residue unit was 58 mol%, and monoisopropyl fumarate residue unit was 42 mol%.

Example 1
88 g of ethyl cellulose (ETHOCEL standard 100 manufactured by Dow Chemical Co., Ltd.), molecular weight Mn=55,000, molecular weight Mw=176,000, Mw/Mn=3.2, total substitution degree DS=2.5 as a resin. Then, 12 g of hexaphenylthiophosphazene obtained in Synthesis Example 1 was dissolved in toluene:methanol=8:2 (weight ratio) to prepare a 20% by weight resin solution, which was drowned on a polyethylene terephthalate film with a coater and dried at a drying temperature of 60. After two-stage drying at 120° C. after 120° C., an optical compensation film (resin composition) having a width of 150 mm was prepared. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are shown in Table 1.

Example 2
88 g of ethyl cellulose used in Example 1 as a resin and 12 g of hexanaphthoxyphosphazene obtained in Synthesis Example 2 were dissolved in toluene:methanol=8:2 (weight ratio) to obtain a 20 wt% resin solution, which was then coated with a coater. It was drowned on a polyethylene terephthalate film, dried at 60° C. and then dried at 120° C. for two steps to prepare an optical compensation film (resin composition) having a width of 150 mm. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 3
88 g of ethyl cellulose used in Example 1 as a resin and 12 g of polydiphenylthiophosphazene obtained in Synthesis Example 3 were dissolved in toluene:methanol=8:2 (weight ratio) to prepare a 20 wt% resin solution, which was then coated with a coater. It was drowned on a polyethylene terephthalate film, dried at 60° C. and then dried at 120° C. for two steps to prepare an optical compensation film (resin composition) having a width of 150 mm. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 4
85 g of ethyl cellulose used in Example 1 as a resin and 15 g of hexaphenoxyphosphazene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in toluene:methanol=8:2 (weight ratio) to give a 20 wt% resin solution, which was then coated with polyethylene terephthalate. After being drowned on the film and dried at a drying temperature of 60° C. and then at two stages at 120° C., an optical compensation film (resin composition) having a width of 150 mm was prepared. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 5
As a resin, 88 g of ethyl cellulose used in Example 1 and 12 g of hexachlorophosphazene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in toluene:methanol=8:2 (weight ratio) to prepare a 20 wt% resin solution, which was then coated with a polyethylene terephthalate film. The solution was dripped on the surface, dried at 60° C. and then dried at 120° C. for two steps to prepare an optical compensation film (resin composition) having a width of 150 mm. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 6
90 g of polycarbonate (Made by Mitsubishi Gas Chemical Co., Inc., Upizeta FPC-2136, molecular weight Mn=29,000, molecular weight Mw=51,000, Mw/Mn=1.8) as resin, and hexaphenylthiophosphazene obtained in Synthesis Example 1 10 g was dissolved in toluene to give a 30% by weight resin solution, which was drooled on a polyethylene terephthalate film with a coater, and after drying at 60° C. and two-stage drying at 120° C., an optical compensation film with a width of 150 mm (resin composition Was manufactured. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 7
50 g of ethyl cellulose used in Example 1, 48 g of diisopropyl fumarate/monoisopropyl fumarate copolymer obtained in Synthesis Example 4, and 2 g of hexaphenylthiophosphazene were dissolved in methylene chloride:acetone=8:2 (weight ratio). 18% by weight as a resin solution, and was sprayed on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diisopropyl fumarate/monoisopropyl fumarate copolymer: 48% by weight, hexaphenylthiophosphazene 2% by weight). It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at 138° C. (thickness after stretching 35 μm). The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Example 8
50 g of ethyl cellulose used in Example 1, 47 g of diisopropyl fumarate/monoisopropyl fumarate copolymer obtained in Synthesis Example 4, and 3 g of hexaphenylthiophosphazene were dissolved in methylene chloride:acetone=8:2 (weight ratio). 18% by weight as a resin solution, and was sprayed on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 50% by weight, Diisopropyl fumarate/monoisopropyl fumarate copolymer: 47% by weight, hexaphenylthiophosphazene 3% by weight). It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into a 50 mm square and uniaxially stretched 2.0 times at 135° C. (thickness after stretching 40 μm). The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

Comparative Example 1
100 g of the ethyl cellulose used in Example 1 as a resin was dissolved in toluene:methanol=8:2 (weight ratio) to give a 20 wt% resin solution, which was drowned on a polyethylene terephthalate film with a coater and dried at a temperature of 60° C. After two-stage drying at 120° C., an optical compensation film (resin composition) having a width of 150 mm was prepared. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

The optical compensation film using ethyl cellulose containing no phosphazene compound did not have reverse wavelength dispersion.

Comparative example 2
As a resin, 100 g of the polycarbonate used in Example 6 was dissolved in toluene to give a 30% by weight resin solution, which was drowned on a polyethylene terephthalate film with a coater and dried at 60° C. and then at 120° C. for two steps. An optical compensation film (resin composition) having a width of 150 mm was produced. It was confirmed that the obtained optical compensation film had no coloring.

The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at a predetermined stretching temperature (thickness after stretching 25 μm).

The retardation characteristics and wavelength dispersion characteristics of the obtained optical compensation film were measured. The results are also shown in Table 1.

The optical compensation film using the polycarbonate containing no phosphazene compound had a larger forward wavelength dispersibility as compared with the film containing the phosphazene compound.

Comparative Example 3
67 g of ethyl cellulose used in Example 1 and 83 g of diisopropyl fumarate/monoisopropyl fumarate copolymer obtained in Synthesis Example 4 were dissolved in methylene chloride:acetone=8:2 (weight ratio) to give a resin of 18% by weight. The solution was poured on a polyethylene terephthalate film with a coater and dried at a drying temperature of 25° C. to obtain an optical compensation film (resin composition) having a width of 150 mm (ethyl cellulose: 45% by weight, diisopropyl fumarate/fumaric acid). Monoisopropyl copolymer: 55% by weight). The obtained optical compensation film was cut into 50 mm square and uniaxially stretched 2.0 times at 150° C. (thickness after stretching 40 μm). The light transmittance, haze, retardation property, and wavelength dispersion property of the obtained optical compensation film were measured. The results are also shown in Table 1.

The film thickness is thicker than that in Example 7 (when the same reverse wavelength dispersion is provided as in Comparative Example 3), and the reverse wavelength dispersion is larger than that in Example 8 (when the same film thickness as in Comparative Example 3). It was inferior in sex.

The wavelength dispersion adjusting agent of the present invention can be used as a wavelength dispersion adjusting agent for imparting (or exhibiting) reverse wavelength dispersion or reducing forward wavelength dispersion.

A resin composition containing such a wavelength dispersion adjusting agent is often particularly excellent in optical characteristics, and thus is useful as a molded article for optical use (optical molded article). Examples of the optical molded product made of such a resin composition include an optical film and an optical lens.

As the optical film, in addition to the retardation film, a polarizing film (and a polarizing element and a polarizing plate protective film forming the same), an alignment film (alignment film), a viewing angle compensation film, a diffusion film, a prism sheet, a light guide plate, a brightness Improvement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF), electromagnetic wave shielding Examples thereof include (EMI) film, electrode substrate film, color filter substrate film, barrier film, color filter layer, black matrix layer, and adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film used for a device display. Specific examples of the display member (or display) provided with the optical film of the present invention include FPD devices such as monitors for personal computers, televisions, mobile phones, car navigation systems, and touch panels (for example, , LCD, PDP, OLED, etc.) and the like.

Claims (9)

A wavelength dispersion adjusting agent comprising a cyclic phosphazene compound represented by the following general formula (1) and/or a compound having a phosphazene skeleton, which is a linear phosphazene compound represented by the following general formula (2). ..
(In the formula, R ₁ , R ₂ , R _{3, and} R ₄ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkylthio group, an arylthio group, chlorine, bromine, Represents a group selected from iodine, and m and n together represent an integer of 3 to 25.)
(In the formula, R ₅ , R ₆ , R ₇ , and R ₈ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkylthio group, an arylthio group, chlorine, bromine, Represents a group selected from iodine, and k and l together represent an integer of 3 to 10000.) The compound having a phosphazene skeleton is a cyclic phosphazene compound in which any one of R ₁ , R ₂ , R ₃ and R ₄ is an aryloxy group, and/or any one of R ₅ , R ₆ , R ₇ and R ₈ is aryl. The wavelength dispersion adjusting agent according to claim 1 , which is a linear phosphazene compound having an oxy group. The compound having a phosphazene skeleton is a cyclic phosphazene compound in which any one of R ₁ , R ₂ , R ₃ and R ₄ is an arylthio group, and/or any one of R ₅ , R ₆ , R ₇ and R ₈ is an arylthio group. The chromatic dispersion adjusting agent according to claim 1 , which is a linear phosphazene compound of A compound having a phosphazene skeleton is a cyclic phosphazene compound in which any of R ₁ , R ₂ , R ₃ and R ₄ is a substituted amino group, and/or one of R ₅ , R ₆ , R ₇ and R ₈ is substituted. The wavelength dispersion adjusting agent according to claim 1 , which is a linear phosphazene compound having an amino group. A resin composition comprising 0.01 to 30% by weight of the wavelength dispersion adjusting agent according to any one of claims 1 to 4 , and 70 to 99.9% by weight of a resin. Resin is cyclic olefin resin, (meth)acrylic resin, styrene resin, cinnamic acid ester resin, fumarate ester resin, polycarbonate resin, polyester resin, cellulose resin, polyphenylene ether resin, poly The resin composition according to claim 5 , which is at least one selected from an ether sulfone resin, a polysulfone resin, and a polymaleimide resin. An optical film comprising the resin composition according to claim 5 or 6, and having a thickness of 5 to 200 μm. The resin composition according to any one of claims 5 to 7 is used, the thickness is 5 to 200 µm, and the in-plane retardation (Re) represented by the following formula (a) is 80 to 300 nm. An optical film characterized in that
Re=(nx−ny)×d (a)
(In the formula, nx represents the refractive index in the slow axis direction in the film plane, ny represents the refractive index in the fast axis direction in the film plane, nz represents the refractive index out of the film plane, and d represents the film. Indicates the thickness.) The ratio Re(450)/Re(550) of the phase difference at the measurement wavelength of 450 nm and the phase difference at the measurement wavelength of 550 nm is 0.60<Re(450)/Re(550)<1.05. Item 9. The optical film according to item 8 .