CN101512397A

CN101512397A - Retardation film, and liquid crystal display device using the same

Info

Publication number: CN101512397A
Application number: CNA2007800316479A
Authority: CN
Inventors: 小松伸一; 庄古利克; 上抚忠广
Original assignee: Nippon Oil Corp
Current assignee: Eneos Corp
Priority date: 2006-08-25
Filing date: 2007-08-20
Publication date: 2009-08-19
Anticipated expiration: 2027-08-20
Also published as: JP2008052119A; CN101512397B; JP4799320B2

Abstract

The present invention provided is a retardation film produced by stretching a film comprising a norbornene ring-opening polymer, wherein the norbornene ring-opening polymer contains a constituent unit (A) represented by the general formula (1) and the constituent unit (A) contains 35 to 100 mol% inclusive of a constituent unit (A-1) which is a type of the constituent unit (A) wherein the wavy line c in the formula (1) shows an exo-type configuration. (1) wherein n represents an integer of 0 or 1; X<1> represents a group represented by the formula: -CH=CH- or a group represented by the formula: -CH2CH2-; R<1>, R<2>, R<3> and R<4> independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have at least one linking group selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, and a polar group; the wavy lines a and b independently represents an endo- or exo-type configuration; and the wavy line c represents an endo- or exo-type configuration.

Description

Phase retardation film and the liquid crystal indicator that uses it

Technical field

The present invention relates to phase retardation film and the liquid crystal indicator that uses it, relate to phase retardation film that can be suitable for 1/2 λ plate, 1/4 λ plate, diaphragm, antireflection film etc. and the liquid crystal indicator that uses it in more detail.

Background technology

In LCD liquid crystal indicators such as (LCD), be purpose with the optical compensation, utilize the optically anisotropic phase retardation film of control, main in the past the material that is called polycarbonate and cyclic polyolefin that uses with positive birefringence.

Under such situation, the norborene class ring-opening polymerization polymer that to have developed with reactive extra high norbornene derivative in cyclic polyolefin be precursor, for example, open the spy that 2003-255102 communique (document 1), spy are opened 2004-176051 communique (document 2), the spy opens and discloses the optical film that is formed by specific norborene class ring-opening polymerization polymer in the 2004-323489 communique (document 3).But the class of the norborene like that in the past ring-opening polymerization polymer of record is insufficient high with the adaptation of other material in document 1～3, in addition, can not fully reach the negative birefringence that expectation is used in the long dispersion membrane of head sea etc.

On the other hand, at No. 5612801 communique of United States Patent (USP) (document 4) even in the negative A phase retardation film of the what is called that also shows special optical characteristics in negative birefringence is disclosed.But, so existing material that is called polystyrene and polymethylmethacrylate with negative birefringence, thermotolerance is insufficient high, in addition, is difficult to obtain negative A phase retardation film with such material.

In addition, also carried out LCD and CD with purposes such as sensors in necessary visible region Zone Full (give phase retardation film (the wide region polarizer: the various researchs long dispersible film of head sea) of 1/4 wavelength phase differential in 400～800nm) the extensive wavelength region may.For example, open in the flat 10-68816 communique (document 5), disclose 2 phase retardation films at the phase retardation film of the direction applying lamination of quadrature almost the spy.In addition, open the phase retardation film that discloses the polycondensation demonstration intrinsic birefringent 2 kinds of monomers of plus or minus in the 2002-48919 communique (document 6) and obtained the spy.Also open to disclose in the 2001-194527 communique (document 7) and will show the intrinsic birefringent polymkeric substance of positive and negative alloying and the phase retardation film that obtains each other, open the spy and disclose after polymerization in the 2005-36201 communique (document 8), will show open loop (being total to) polymerization of the intrinsic birefringent 2 kinds of norborneol vinyl monomers of plus or minus and the phase retardation film that obtains the spy.

But, about such phase retardation film of document 5 records, need to use 2 films of bonding agent applying during fabrication, there are manufacturing process's complexity, decrease in yield, cost to uprise the problem of isoproductivity aspect.In addition, about the such existing phase retardation film of record in the document 6～8, under the situation of mixing during fabrication, polymkeric substance is difficult to mix each other, and therefore mostly occurring greatly is separated, produces gonorrhoea, is difficult to use in optical applications the phase retardation film that obtains.In addition, make these phase retardation films and the monomer of the demonstration negative birefringence used has special structure, therefore also have it to make the problem of difficulty, high price.

Summary of the invention

The present invention is the invention that forms in view of the problem of above-mentioned prior art existence, purpose is to provide individual layer to have high transparent and excellent wavelength dispersion characteristic, can give specific phase differential to the light of wide region, very high with the adaptation of other material, even in negative birefringence, also can reach optical characteristics, and can make birefringent wavelength dispersion characteristic become contrary phase retardation film that disperses and the liquid crystal indicator that uses this phase retardation film as special negative A.

The inventor etc. further investigate in order to achieve the above object repeatedly, it found that and uses the norborene class ring-opening polymerization polymer that contains the structural unit of representing with the ad hoc structure formula, the exo isomer ratio of the said structure unit that will contain in this polymkeric substance is made as particular range, can access individual layer thus and have high transparent and excellent wavelength dispersion characteristic, light to wide region can give specific phase differential, very high with the adaptation of other material, even in negative birefringence, also can reach optical characteristics as special negative A, and can make birefringent wavelength dispersion characteristic become the contrary phase retardation film that disperses, so far finish the present invention.

That is, phase retardation film of the present invention stretches the film that is formed by norborene class ring-opening polymerization polymer and obtains,

This norborene class ring-opening polymerization polymer contains the structural unit (A) shown in the following general formula (1), and in said structure unit (A), following wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles more than the %, the 100 moles scopes below the %

[in the formula (1), n represents 0 or 1 integer,

X ¹Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ¹, R ², R ³And R ⁴Can be identical or different, expression is selected from any one atom or the base in hydrogen atom, halogen atom, alkyl and the polar group respectively, above-mentioned alkyl is to have at least a kind of alkyl that is connected the carbon number 1～30 of basic replacement or non-replacement that is selected from oxygen atom, nitrogen-atoms, sulphur atom and the silicon atom

The spatial configuration of type or external form in wave-like line a, b represent,

The spatial configuration of type or external form in wave-like line c represents.]

Phase retardation film of the present invention like this can make birefringent wavelength dispersion characteristic become contrary the dispersion.Then, from bringing into play so contrary dispersed viewpoint, phase retardation film as the invention described above, in said structure unit (A), above-mentioned wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles of scopes, and the preferably contrary phase retardation film that disperses of above-mentioned phase retardation film more than the %, less than 65 moles of %.

About the phase retardation film of the invention described above, even in negative birefringence, also can reach the optical characteristics of special negative A.And, from reaching viewpoint as the optical characteristics of negative A, phase retardation film as the invention described above, in said structure unit (A), above-mentioned wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 65 moles more than the %, the 100 moles scopes below the %, and the preferably negative A phase retardation film of above-mentioned phase retardation film.

In addition, the optical characteristics of the negative A of so-called conduct, refer to draw direction with the uniaxial tension of above-mentioned film when being defined as X-axis and will being defined as Y-axis and Z axle with the direction of X-axis quadrature, the refractive index (Ny) of the refractive index of X-axis (Nx), Y-axis and the refractive index (Nz) of Z axle satisfy the relation shown in the following relational expression (1):

Ny＝Nz>Nx (1)。

Therefore, phase retardation film of the present invention preferably satisfies the condition shown in the above-mentioned relation formula (1).And, if utilize the negative A phase retardation film satisfy such condition, to being that improve at the visual angle of TFT-LCD, the TN-TFT of difficulty and tone improvement etc. just becomes possibility in the past.

In addition, about the phase retardation film of the invention described above, the X in the above-mentioned general formula (1) ¹Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, with respect to preferably 90 moles more than the % of the entire infrastructure unit in the above-mentioned norborene class ring-opening polymerization polymer.

In addition, phase retardation film about the invention described above, above-mentioned norborene class ring-opening polymerization polymer can be the norborene class ring opening copolymer thing that also contains the structural unit (B) shown in the following general formula (3), at this moment, said structure unit (A) is the structural unit (A ') shown in the following general formula (2), and the spatial configuration of the replacement in the following general formula (2) or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio, with respect to the total amount of structural unit (A ') preferably in 90 moles of scopes more than the %.Promptly, phase retardation film about the invention described above, above-mentioned norborene class ring-opening polymerization polymer is norborene class ring opening copolymer thing preferably, this norborene class ring opening copolymer thing contains the structural unit (B) shown in structural unit (A ') shown in the following general formula (2) and the following general formula (3), and in said structure unit (A '), the spatial configuration of the replacement in the above-mentioned general formula (2) or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio in 90 moles of scopes more than the %.

[in the formula (2), n, X ¹, R ¹, R ², R ³, R ⁴With n, the X in wave-like line c and the above-mentioned general formula (1) ¹, R ¹, R ², R ³, R ⁴Same meaning with wave-like line c.]

[in the formula (3), n represents 0 or 1 integer,

X ²Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ⁵, R ⁶, R ⁷, R ⁸Can be identical or different, respectively expression be selected from alkyl, the carbon number 1～20 of hydrogen atom, halogen atom, cyano group, carbon number 1～20 thiazolinyl, carbon number 1～20 alkyl-carbonyl and have any one atom or base in the ester group of alkyl of carbon number 1～20

R ⁵～R ⁸In mutually combine more than 2, can form the monocyclic hydrocarbon of the carbon number 3～20 that can have unsaturated link, maybe can have the polycycle hydrocarbon of the carbon number 4～20 of unsaturated link,

R ⁵And R ⁶, or, R ⁷And R ⁸Can form the alkylidene of carbon number 1～20 together.]

Like this, in the present invention, as above-mentioned norborene class ring-opening polymerization polymer, use contains the structural unit (B) shown in structural unit (A ') shown in the above-mentioned general formula (2) and the above-mentioned general formula (3), and when the ratio that makes said structure unit (A '-1) is the norborene class ring opening copolymer thing of particular range, individual layer has high transparent and excellent wavelength dispersion characteristic, light to wide region can give specific phase differential, very high with the adaptation of other material, and, even in negative birefringence, also can reach optical characteristics, and can make birefringent wavelength dispersion characteristic become contrary the dispersion as special negative A.

In addition, phase retardation film about the invention described above, even at above-mentioned norborene class ring-opening polymerization polymer is to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B), also can make birefringent wavelength dispersion characteristic become contrary the dispersion.And, at above-mentioned norborene class ring-opening polymerization polymer is to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B), from bringing into play so contrary dispersed viewpoint, phase retardation film as the invention described above, the ratio of said structure unit (A '-1) with respect to the entire infrastructure unit in the above-mentioned norborene class ring opening copolymer thing in 40 moles of scopes more than the %, less than 80 moles of %, and, the preferably contrary phase retardation film that disperses of above-mentioned phase retardation film.

In addition, phase retardation film about the invention described above, even at above-mentioned norborene class ring-opening polymerization polymer is to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B), even in negative birefringence, also can reach optical characteristics as special negative A.And, at above-mentioned norborene class ring-opening polymerization polymer is to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B), from reaching viewpoint as the optical characteristics of negative A, phase retardation film as the invention described above, the ratio of said structure unit (A '-1) with respect to the entire infrastructure unit in the above-mentioned norborene class ring opening copolymer thing in 80 moles more than the %, the 99 moles scopes below the %, and, the preferably negative A phase retardation film of above-mentioned phase retardation film.

In addition, as mentioned above, the optical characteristics of the negative A of so-called conduct, refer to and satisfy the relation shown in the above-mentioned relation formula (1), therefore, preferably satisfy the condition shown in the above-mentioned relation formula (1) as phase retardation film of the present invention even be to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B) at above-mentioned norborene class ring-opening polymerization polymer.

In addition, be to contain under the situation of above-mentioned norborene class ring opening copolymer thing of structural unit (A ') and structural unit (B) at above-mentioned norborene class ring-opening polymerization polymer, about the phase retardation film of the invention described above, the X in the above-mentioned general formula (2) ¹Be formula-CH ₂CH ₂-shown in the structural unit of base and the X in the above-mentioned general formula (3) ²Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, with respect to preferably 90 moles more than the % of the entire infrastructure unit in the above-mentioned norborene class ring-opening polymerization polymer.

In addition, liquid crystal indicator of the present invention is characterised in that to have the phase retardation film of the invention described above.

According to the present invention, can provide individual layer to have high transparent and excellent wavelength dispersion characteristic, light to wide region can give specific phase differential, very high with the adaptation of other material, even in negative birefringence, also can reach optical characteristics as special negative A, and make birefringent wavelength dispersion characteristic become the contrary phase retardation film that disperses, and the liquid crystal indicator that uses this phase retardation film.

In addition, such phase retardation film of the present invention can filming.Phase retardation film of the present invention, its manufacturing process also is simplified, and can make with high finished product rate, low cost.

Description of drawings

Fig. 1 is the NMR figure of the hydride (HpA) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 1.

Fig. 2 is the NMR figure of the hydride (HpB) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 1.

Fig. 3 is the NMR figure of the hydride (HpC) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 2.

Fig. 4 is the NMR figure of the hydride (HpD) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 2.

Fig. 5 is the NMR figure of the hydride (HpE) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 3.

Fig. 6 is the NMR figure of the hydride (HpF) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 4.

Fig. 7 is that expression is about the external form ratio of the stretched film that obtains in embodiment 1, embodiment 3～5, embodiment 7～8 and the chart of birefringent relation.

Fig. 8 is expression about the chart of the relation of the external form ratio of the stretched film that obtains in embodiment 1, embodiment 3～5, embodiment 7～8 and birefringence wavelength dispersion value.

Fig. 9 is the NMR figure of the hydride (HpI) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 7.

Figure 10 is the NMR figure of the hydride (HpJ) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 8.

Figure 11 is the NMR figure of the hydride (HpK) of the norborene class ring-opening polymerization polymer that obtains in synthesis example 9.

Figure 12 is that expression is about the copolymerization ratio of the stretched film that obtains in embodiment 9～13 and the chart of birefringent relation.

Figure 13 is expression about the chart of the relation of the copolymerization ratio of the stretched film that obtains in embodiment 9～13 and birefringence wavelength dispersion value.

Figure 14 is expression about the chart of the relation of the copolymerization ratio of the stretched film that obtains in embodiment 9～13 and Tg.

Embodiment

Below, preferred embodiment explain the present invention according to it.

Phase retardation film of the present invention at first is described.That is, phase retardation film of the present invention stretches the film that is formed by norborene class ring-opening polymerization polymer and obtains,

[in the formula (1), n represents 0 or 1 integer,

X ¹Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

As the norborene class ring-opening polymerization polymer that the present invention relates to, can enumerate the structural unit (A) that contains shown in the above-mentioned general formula (1), its substituting group has aromatic rings, direct combination of cyclopentane ring that is obtained by the ring-opening polymerization of norbornene monomer in addition and aromatic rings or the norborene class ring-opening polymerization polymer that closes by two loops.

In addition, in such structural unit (A), the n in the above-mentioned general formula (1) represents 0 or 1 integer.And, as above-mentioned norborene class ring-opening polymerization polymer, can be to be the homopolymer that 0 or 1 structural unit (A) constitutes by the n in the above-mentioned general formula (1), also can be that n in the above-mentioned general formula (1) is that 0 structural unit (A) and the n in the above-mentioned general formula (1) are the multipolymer of 1 structural unit (A).Such n value is used for optical characteristics and every rerum natura of the norborene class ring-opening polymerization polymer that control fully evenly obtains, and can suitably adjust according to the design of purpose.That is,, can suitably form different norborene class ring opening copolymer things according to purpose by the such n value of suitable change.

In addition, the spatial configuration of type or external form in wave-like line a, the b in the above-mentioned general formula (1) represents.In the present invention, in the entire infrastructure unit (A) in above-mentioned norborene class ring-opening polymerization polymer (with respect to the total amount of structural unit (A)), the spatial configuration that above-mentioned wave-like line a, b represent be external form structural unit ratio preferably 35～100 moles of %, be more preferably 65～100 moles.Such wave-like line a, the spatial configuration that b represents be external form structural unit contain ratio less than 35 moles of % the time, the tendency that does not show contrary dispersing characteristic is arranged, in addition, be 65 moles of % when following, just have not show the tendency of bearing A.

The spatial configuration of type or external form in wave-like line c in the above-mentioned general formula (1) also represents.In the present invention, in the entire infrastructure unit (A) in above-mentioned norborene class ring-opening polymerization polymer, above-mentioned wave-like line c represents that the ratio that contains of the structural unit (A-1) of external form spatial configuration is 35～100 moles of %.Such wave-like line c represents the ratio of the structural unit (A-1) of external form spatial configuration, with respect to the total amount of structural unit (A) during less than 35 moles of %, the wavelength dispersion value (D=Δ n (λ=481nm)/Δ n (λ=589nm)) becomes the scope more than 0.92, less than 1.0, just can not obtain showing the wavelength dispersion value less than 0.92 or the wavelength dispersion value become the contrary film that disperses the special optical characteristics of (D is more than 1.0).In addition, wave-like line c represents the spatial configuration of external form, is meant that the spatial configuration of the phenyl of the replacement of combination on wave-like line c or non-replacement is the external form coordination.In addition, as the assay method of birefringence n, can adopt the trade name of using prince's instrumentation society to produce as determinator: " KOBRA21DH " carries out method for measuring.

In addition, about such phase retardation film of the present invention, from reaching the long dispersed viewpoint of head sea, above-mentioned wave-like line c represents the ratio of the structural unit (A-1) of the spatial configuration of external form, with respect to the total amount of the structural unit (A) in the above-mentioned norborene class ring-opening polymerization polymer preferably in 35 moles of scopes more than the %, less than 65 moles of % (more preferably in the scope of 40 moles of %～60 mole %).Promptly, as phase retardation film of the present invention, total amount with respect to structural unit (A), make above-mentioned wave-like line c represent that the ratio of the structural unit of the spatial configuration of external form (A-1) is more than 35 moles of %, less than the scope of 65 moles of %, can make above-mentioned phase retardation film become the contrary phase retardation film that disperses thus.Such wave-like line c represents that the ratio of structural unit of the spatial configuration of external form is 65 moles of % when above with respect to the total amount of structural unit (A), and it is long dispersed to be difficult to reach head sea.

In addition, about phase retardation film of the present invention, from reaching the viewpoint of the optical characteristics of bearing A, above-mentioned wave-like line c represents the ratio of the structural unit (A-1) of the spatial configuration of external form, in the entire infrastructure unit (A) in above-mentioned norborene class ring-opening polymerization polymer, preferably in the scope of 65～100 moles of % (more preferably 70～100 moles of %).Promptly, as phase retardation film of the present invention, total amount with respect to the structural unit (A) in the above-mentioned norborene class ring-opening polymerization polymer, make above-mentioned wave-like line c represent that the ratio of the structural unit of the spatial configuration of external form (A-1) is the scope of 65～100 moles of %, can make above-mentioned phase retardation film become negative A phase retardation film thus.Such wave-like line c represents the ratio of the structural unit (A-1) of the spatial configuration of external form, during with respect to the total amount of the structural unit (A) in the above-mentioned norborene class ring-opening polymerization polymer, less than 65 moles of %, even the tendency that can not reach in negative birefringence as the optical characteristics of special negative A is arranged.And, as so negative A phase retardation film, when the draw direction with the uniaxial tension of above-mentioned film was defined as X-axis and will be defined as Y-axis and Z axle with the direction of X-axis quadrature, the refractive index (Ny) of the refractive index of X-axis (Nx), Y-axis and the refractive index (Nz) of Z axle preferably satisfied the relation shown in the following relational expression (1):

Ny＝Nz>Nx (1)。

In addition, as the assay method of above-mentioned refractive index (Nx, Ny and Nz), can adopt as the determinator of refractive index and use the trade name " 2010 PrismCoupler " of Metricon society production, the method for mensuration refractive index.

In addition, with such wave-like line a, b, the spatial configuration that c represents, the reaction treatment after reaction conditions in the time of can being made by monomer and the manufacturing etc. is suitably adjusted.For example, the spatial configuration of wave-like line a, b can be handled control easily by the isomerization after making, and the thermal treatment after reaction conditions the when spatial configuration of wave-like line c can be made by monomer and the manufacturing is controlled.

In addition, with the R in the above-mentioned general formula (1) ¹, R ², R ³, R ⁴The substituting group of expression can be identical or different, be respectively any one atom or the base that is selected from hydrogen atom, halogen atom, alkyl and the polar group, above-mentioned alkyl is to have the alkyl that at least a kind of being selected from oxygen atom, nitrogen-atoms, sulphur atom and the silicon atom is connected the carbon number 1～30 (more preferably 1～10) of the replacement or the non-replacement of base.

In addition, as such R ¹, R ², R ³, R ⁴Can select, can have at least a kind of being selected from oxygen atom, nitrogen-atoms, sulphur atom and the silicon atom and be connected the replacement of base or the alkyl of non-alternate c atoms several 1～30, the alkyl of more preferably above-mentioned carbon number 1～10.In addition, can be the alkyl of straight chain shape, a chain or ring-type as such alkyl, be not particularly limited, can enumerate alkyl, naphthenic base, thiazolinyl, alkynyl, phenyl, aryl etc.In addition, viewpoint from the transparency and weatherability, such alkyl preferred alkyl, naphthenic base, phenyl, aryl etc., the phase retardation film that obtains from utilization can be given the transparency of height and the viewpoint of weatherability, alkyl such as special preferred tertiary butyl in above-mentioned substituting group.In addition, as the straight chain shape alkyl of the preferred carbon number 1～5 of such alkyl or a chain alkyl of carbon number 3～7.In addition, as the preferred saturated hydrocarbyl of such alkyl.

In addition, as R ¹, R ², R ³, R ⁴The polar group that can select for example can be enumerated hydroxyl, sulfydryl, cyano group, amino, carboxyl, sulfonic group, ester group etc.Can give stable on heating viewpoint highly from the phase retardation film that utilization obtains, as the R in such general formula (1) ¹, R ², R ³, R ⁴Shown substituting group, preferred cyano group etc. in above-mentioned substituting group, from the viewpoint of the transparency and weatherability, preferred ester group etc.

In addition, the monomer that uses when making above-mentioned norborene class ring-opening polymerization polymer obtain easiness viewpoints such as (manufacturing efficient), as the R in the above-mentioned general formula (1) ¹, R ², R ³More preferably be respectively hydrogen atom, fluorine atom, chlorine atom, especially preferably hydrogen atom independently.In addition, the monomer that uses when making above-mentioned norborene class ring-opening polymerization polymer obtain easiness viewpoints such as (manufacturing efficient), as the R in the above-mentioned general formula (1) ⁴, be more preferably the chain alkyl (be more preferably a chain alkyl of carbon number 3～5, especially preferably the tert-butyl group) of carbon number 3～7.

In addition, the X in the above-mentioned general formula (1) ¹Be the base shown in formula-CH=CH-or formula-CH ₂CH ₂-shown in base.In the norborene class ring-opening polymerization polymer that the present invention relates to, the X in the entire infrastructure unit (A) that is contained ¹Can only constitute, also can and constitute by the structural unit that possesses above-mentioned base respectively (A) mixing by 1 above-mentioned base.In addition, the norborene class ring-opening polymerization polymer that the present invention relates to, the hydrogenation ratio is high more, and promptly the two keys in the main chain are few more, just become more stable polymer more.Therefore, as the norborene class ring-opening polymerization polymer that the present invention relates to, preferably by the few polymkeric substance of two keys in fully hydrogenation, the main chain.From such viewpoint, the X in the above-mentioned general formula (1) ¹Formula-CH preferably ₂CH ₂-shown in base.In addition, the X in the above-mentioned general formula (1) ¹Be formula-CH ₂CH ₂-shown in the ratio of structural unit (A) of base, in the entire infrastructure unit of above-mentioned norborene class ring-opening polymerization polymer (A), be preferably more than 90 moles of % (more preferably 95 moles of %, preferred especially 98 moles of %).Such ratio is during less than 90 moles of %, and the stability decreases of polymkeric substance has the tendency that is difficult to suppress the painted and deterioration that causes because of heat.

In addition, in the present invention, above-mentioned norborene class ring-opening polymerization polymer is norborene class ring opening copolymer thing preferably, this norborene class ring opening copolymer thing contains the structural unit (B) shown in structural unit (A ') shown in the following general formula (2) and the following general formula (3), and in said structure unit (A '), the spatial configuration of the replacement in the above-mentioned general formula (2) or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio in 90 moles of scopes more than the %.

[in the formula (3), n represents 0 or 1 integer,

X ²Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

In the above-mentioned general formula (2), n, X ¹, R ¹, R ², R ³, R ⁴With n, the X in wave-like line c and the above-mentioned general formula (1) ¹, R ¹, R ², R ³, R ⁴Same meaning with wave-like line c.In addition, said structure unit (A '-1) is the structural unit that wave-like line c in the above-mentioned general formula (2) represents the spatial configuration of external form.

In addition, the same meaning of n in the above-mentioned general formula (3) and the n in the above-mentioned general formula (1).In addition, the X in the above-mentioned general formula (3) ²With the X in the above-mentioned general formula (1) ¹Same meaning.

In addition, the R in the above-mentioned general formula (3) ⁵, R ⁶, R ⁷, R ⁸Shown substituting group can be identical or different, be respectively the alkyl that is selected from hydrogen atom, halogen atom, cyano group, carbon number 1～20, carbon number 1～20 thiazolinyl, carbon number 1～20 alkyl-carbonyl and have any one atom or base in the ester group of alkyl of carbon number 1～20.In addition, R ⁵～R ⁸In mutually combine more than 2, can form the monocyclic hydrocarbon of the carbon number 3～20 that can have unsaturated link, maybe can have the polycycle hydrocarbon of the carbon number 4～20 of unsaturated link, R ⁵And R ⁶Can form the alkylidene of carbon number 1～20 together, perhaps R ⁷And R ⁸Can form the alkylidene of carbon number 1～20 together.

As the alkyl of such carbon number 1～20 (more preferably 1～10), can be the alkyl of straight chain shape, a chain or ring-type, be not particularly limited, but from the viewpoint of the transparency and weatherability, preferable methyl and ethyl etc.In addition, if the carbon number of such alkyl greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, as the thiazolinyl of above-mentioned carbon number 1～20 (more preferably 1～10), can be the thiazolinyl of straight chain shape, a chain or ring-type, be not particularly limited, but from the viewpoint of the transparency and weatherability, preferably ethylidene etc.In addition, if the carbon number of such thiazolinyl greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, as the alkyl-carbonyl of above-mentioned carbon number 1～20 (more preferably 1～10), can be the alkyl-carbonyl of straight chain shape, a chain or ring-type, be not particularly limited, but from the viewpoint of the transparency and weatherability, preferable methyl carbonyl and ethyl carbonyl etc.In addition, if the carbon number of such alkyl-carbonyl greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, as above-mentioned ester group with alkyl of carbon number 1～20 (more preferably 1～10), can be the ester group of straight chain shape, a chain or ring-type, be not particularly limited, but from the viewpoint of the transparency and weatherability, preferred methoxycarbonyl and ethoxy carbonyl etc.In addition, if the carbon number of such ester greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, the monocyclic hydrocarbon as the above-mentioned carbon number 3～20 that can have a unsaturated link (more preferably 3～10) is not particularly limited, and can also have other substituting group.From the viewpoint of the transparency and weatherability, as such monocyclic hydrocarbon cyclopentene and cyclohexene etc.In addition, if the carbon number of such monocyclic hydrocarbon greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, the polycycle hydrocarbon as the above-mentioned carbon number 4～20 that can have a unsaturated link (more preferably 4～12) is not particularly limited, and can also have other substituting group.From the viewpoint of the transparency and weatherability, as so preferred naphthalene of polycycle hydrocarbon and biphenyl etc.In addition, if the carbon number of such polycycle hydrocarbon greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, the alkylidene as above-mentioned carbon number 1～20 (more preferably 1～10) is not particularly limited, but from the viewpoint of the transparency and weatherability, preferably indane, tetralin etc.In addition, if the carbon number of such alkylidene greater than the above-mentioned upper limit, just is difficult to by distillation, method such as crystallization is made with extra care again.

In addition, the norborene class ring-opening polymerization polymer that the present invention relates to is that above-mentioned norborene class ring opening copolymer thing has phenyl or the substituted-phenyl from said structure unit (A ') when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B) in substituting group.Also because such norborene class ring opening copolymer thing is the multipolymer that can be obtained by the ring-opening polymerization of norbornene monomer (raw material of said structure unit (A ') and said structure unit (B)), so become the directly combination or close the multipolymer that forms by two loops of cyclopentane ring and above-mentioned phenyl or substituted-phenyl.

In containing the above-mentioned norborene class ring opening copolymer thing of such structural unit (A ') and structural unit (B), the replacement in the above-mentioned general formula (2) or the phenyl (R of non-replacement ⁴In conjunction with phenyl ring) spatial configuration be the external form coordination structural unit (A '-1) contain ratio, in the scope of total amount more than 90 moles of % (more preferably 95 moles of %) with respect to the structural unit (A ') that contains in the above-mentioned norborene class ring opening copolymer thing.In such norborene class ring opening copolymer thing, the ratio that contains of the said structure unit in said structure unit (A ') (A '-1) is prescribed a time limit down less than above-mentioned, is difficult to make the optical characteristics of the film performance purpose that obtains.

In addition, above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), said structure unit (A ') in the above-mentioned norborene class ring opening copolymer thing and said structure unit (B's) contains ratio, in mol ratio (structural unit (A '): structural unit (B)) preferably 99: 1～40: 60, be more preferably 99: 1～50: 50 moles of %.The ratio that contains of such structural unit (A ') is prescribed a time limit down less than above-mentioned, and the tendency that can not show optical characteristics such as contrary dispersing characteristic is arranged.

At above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), with respect to the entire infrastructure unit that is contained in the above-mentioned norborene class ring opening copolymer thing, said structure unit (A '-1) contain ratio preferably 40～99 moles of %, be more preferably 50～99 moles of %.Said structure unit (A '-1) in the above-mentioned norborene class ring opening copolymer thing like this contain ratio less than 40 moles of % the time, the tendency that does not show contrary dispersing characteristic is arranged.In addition, when above-mentioned norborene class ring-opening polymerization polymer is above-mentioned norborene class ring opening copolymer thing, said structure unit (A '-1) contain ratio if 80 moles below the %, the tendency that does not show negative A is just arranged.In addition, above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), the ratio of the said structure unit in the entire infrastructure unit (A '-1) is during less than 40 moles of %, the wavelength dispersion value (D=Δ n (λ=481nm)/Δ n (λ=589nm)) becomes the scope more than 0.92, less than 1.0, have can not get showing the wavelength dispersion value less than 0.92 or the wavelength dispersion value be the tendency of film of the special optical characteristics of high dispersive (D is more than 1.0).

In addition, above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), about the phase retardation film that obtains, from reaching the long dispersed viewpoint of head sea, the spatial configuration of the phenyl of above-mentioned replacement or non-replacement be the external form coordination structural unit (A '-1) contain ratio, with respect to the entire infrastructure unit that is contained in the above-mentioned norborene class ring opening copolymer thing preferably in 40 moles of scopes (more preferably in the scope of 50～70 moles of %) more than the %, less than 80 moles of %.Promptly, when above-mentioned norborene class ring-opening polymerization polymer is above-mentioned norborene class ring opening copolymer thing, the ratio that makes said structure unit (A '-1) is more than 40 moles of %, less than the scope of 80 moles of %, can make above-mentioned phase retardation film become the contrary phase retardation film that disperses thus.The spatial configuration of such phenyl ring is that the ratio of the structural unit (A '-1) of external form is 80 moles of % when above, and it is long dispersed to be difficult to reach head sea.

In addition, at above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), about the phase retardation film that obtains, from reaching the viewpoint of the optical characteristics of bearing A, the spatial configuration of the replacement in the above-mentioned general formula (2) or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio, with respect to the entire infrastructure unit that is contained in the above-mentioned norborene class ring opening copolymer thing preferably in the scope of 80～99 moles of % (more preferably 90～99 moles of %).Promptly, above-mentioned norborene class ring-opening polymerization polymer is when containing the above-mentioned norborene class ring opening copolymer thing of said structure unit (A ') and said structure unit (B), make the scope that ratio is 80～99 moles of % that contains of said structure unit (A '-1), can make above-mentioned phase retardation film become negative A phase retardation film thus.With respect to the entire infrastructure unit in the above-mentioned norborene class ring opening copolymer thing, said structure unit (A '-1) contain ratio less than 80 moles of % the time, about the phase retardation film that obtains, even the tendency that can not reach in negative birefringence as the optical characteristics of special negative A is arranged.And the negative A phase retardation film as so preferably satisfies the relation shown in the above-mentioned relation formula (1).

When above-mentioned norborene class ring-opening polymerization polymer is above-mentioned norborene class ring opening copolymer thing, the X in the above-mentioned general formula (2) ¹Be formula-CH ₂CH ₂-shown in the said structure unit (A ') of base and the X in the above-mentioned general formula (3) ²Be formula-CH ₂CH ₂-shown in base said structure unit (B) contain ratio, with respect to the entire infrastructure unit in the above-mentioned norborene class ring-opening polymerization polymer preferably more than 90 moles of % (more preferably 95 moles of %, preferred especially 98 moles of %).Such ratio is during less than 90 moles of %, and the stability decreases of multipolymer has the tendency that is difficult to suppress the painted and deterioration that causes because of heat.

In addition, in the present invention, the weight-average molecular weight of above-mentioned norborene class ring-opening polymerization polymer preferably 1000～10000000, be more preferably 10000～1000000.The weight-average molecular weight of above-mentioned norborene class ring-opening polymerization polymer is prescribed a time limit down less than above-mentioned, the intensity of the norborene class ring-opening polymerization polymer that obtains has the tendency of step-down, in addition, if greater than the above-mentioned upper limit, the melt viscosity of the norborene class ring-opening polymerization polymer that obtains has the tendency that becomes too high.

Below, the method that the method for the norborene class ring-opening polymerization polymer that the present invention relates to as manufacturing is fit to is described.Method as making such norborene class ring-opening polymerization polymer has no particular limits, and for example, can compatibly adopt the method shown in the following reaction equation (1).

[reaction equation (I)]

[in the above-mentioned reaction equation (I), R ¹, R ², R ³, R ⁴, wave-like line a, wave-like line b, wave-like line c, n respectively with above-mentioned general formula (1) in R ¹, R ², R ³, R ⁴, wave-like line a, wave-like line b, wave-like line c, n same meaning.]

Method with such reaction equation (1) expression, after making the norbornene monomer ring-opening polymerization shown in the above-mentioned general formula (I-1) specifically, obtaining the norborene class ring-opening polymerization polymer shown in the above-mentioned general formula (I-2), the ring-opening polymerization polymer that obtains is carried out hydrogenation and obtain the method for the norborene class ring-opening polymerization polymer shown in the above-mentioned general formula (I-2 ').In addition, the structural unit shown in above-mentioned general formula (I-2) and (I-2 ') is equivalent to said structure unit (A) respectively.

In addition, the above-mentioned norborene class ring opening copolymer thing that contains said structure unit (A ') and said structure unit (B) in manufacturing for example can be fit to adopt the method shown in the following reaction equation (II) during as above-mentioned norborene class ring-opening polymerization polymer.

[reaction equation (II)]

[the R in the reaction equation (II) ¹, R ², R ³, R ⁴, n and wave-like line c respectively with above-mentioned general formula (1) in R ¹, R ², R ³, R ⁴, n and wave-like line c same meaning, the R in the reaction equation (II) ⁵, R ⁶, R ⁷, R ⁸With n respectively with above-mentioned general formula (3) in R ⁵, R ⁶, R ⁷, R ⁸Same meaning with n.]

Method with such reaction equation (II) expression, make the norbornene monomer shown in norbornene monomer shown in the general formula (II-1) in the reaction equation (II) and the general formula (II-2) carry out ring opening copolymer specifically, after obtaining containing the norborene class ring opening copolymer thing of the structural unit shown in above-mentioned general formula (II-3) and (II-4), the ring opening copolymer thing that obtains is carried out hydrogenation, obtain containing the method for the norborene class ring opening copolymer thing of the structural unit shown in above-mentioned general formula (II-3 ') and (II-4 ').In addition, structural unit shown in above-mentioned general formula (II-3) and (II-3 ') is the structural unit that is equivalent to said structure unit (A ') respectively, and the structural unit shown in above-mentioned general formula (II-4) and (II-4 ') is the structural unit that is equivalent to said structure unit (B) respectively.

As the norbornene monomer shown in norbornene monomer shown in the general formula in the above-mentioned reaction equation (I) (I-1) or the general formula (II-1) in the above-mentioned reaction equation (II), for example can enumerate following such norbornene monomer.

5-phenyl two ring [2.2.1]-2-heptene, 8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to tert-butyl group phenyl) two ring [2.2.1]-2-heptene, 8-(to tert-butyl group phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-aminophenyl) two ring [2.2.1]-2-heptene, 8-(p-aminophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(adjacent acetoxyl group phenyl) two ring [2.2.1]-2-heptene, 8-(adjacent acetoxyl group phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the acetoxyl group phenyl) two ring [2.2.1]-2-heptene, 8-(to the acetoxyl group phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-bromo-5-phenyl-two ring [2.2.1]-2-heptene, 8-phenyl-9-bromine Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-isopropyl phenyl) two ring [2.2.1]-2-heptene, 8-(p-isopropyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(bromophenyl) two ring [2.2.1]-2-heptene, 8-(bromophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to bromophenyl) two ring [2.2.1]-2-heptene, 8-(to bromophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(o-bromophenyl) two ring [2.2.1]-2-heptene, 8-(o-bromophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6,6-two fluoro-5-(to bromophenyl) two ring [2.2.1]-2-heptene, 8-(to bromophenyl)-9,9-difluoro Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(rubigan)-5-methyl two ring [2.2.1]-2-heptene, 8-(rubigan)-9-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(Chloro-O-Phenyl) two ring [2.2.1]-2-heptene, 8-(Chloro-O-Phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(chlorphenyl) two ring [2.2.1]-2-heptene, 8-(chlorphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(rubigan) two ring [2.2.1]-2-heptene, 8-(rubigan) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(a chloromethyl phenyl) two ring [2.2.1]-2-heptene, 8-(a chloromethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the chloromethyl phenyl) two ring [2.2.1]-2-heptene, 8-(to the chloromethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，0.0]-3-dodecylene, 5-(to the cyano methyl phenyl) two ring [2.2.1]-2-heptene, 8-(to the cyano methyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(adjacent chloromethyl phenyl) two ring [2.2.1]-2-heptene, 8-(adjacent chloromethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,6-dichlorophenyl) two ring [2.2.1]-2-heptene, 8-(2,6-dichlorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to fluorophenyl)-5-methyl two ring [2.2.1]-2-heptene, 8-(to fluorophenyl)-9-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(adjacent fluorophenyl) two ring [2.2.1]-2-heptene, 8-(adjacent fluorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(fluorophenyl) two ring [2.2.1]-2-heptene, 8-(fluorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to fluorophenyl) two ring [2.2.1]-2-heptene, 8-(to fluorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(pentafluorophenyl group) two ring [2.2.1]-2-heptene, 8-(pentafluorophenyl group) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(o-methoxyphenyl) two ring [2.2.1]-2-heptene, 8-(o-methoxyphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to ethoxyl phenenyl) two ring [2.2.1]-2-heptene, 8-(to ethoxyl phenenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the phenoxy group phenyl) two ring [2.2.1]-2-heptene, 8-(to the phenoxy group phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to hydroxymethyl phenyl) two ring [2.2.1]-2-heptene, 8-(to hydroxymethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-methoxyphenyl) two ring [2.2.1]-2-heptene, 8-(p-methoxyphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(o-methyl-phenyl-) two ring [2.2.1]-2-heptene, 8-(o-methyl-phenyl-) Fourth Ring [4,4.1^2，5.1 ^7，10, 0]-3-dodecylene, 5-(a methyl phenyl) two ring [2.2.1]-2-heptene, 8-(a methyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-methylphenyl) two ring [2.2.1]-2-heptene, 8-(p-methylphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-methyl-5-phenyl two ring [2.2.1]-2-heptene, 8-methyl-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-methyl-5-phenyl two ring [2.2.1]-2-heptene, 9-methyl-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(nitrobenzophenone) two ring [2.2.1]-2-heptene, 8-(nitrobenzophenone) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-nitrophenyl) two ring [2.2.1]-2-heptene, 8-(p-nitrophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the cyano group phenyl) two ring [2.2.1]-2-heptene, 8-(to the cyano group phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(aligning octyl phenyl) two ring [2.2.1]-2-heptene, 8-(aligning octyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-trimethyl siloxy-5-phenyl two ring [2.2.1]-2-heptene, 8-(trimethyl siloxy)-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,4,6-trimethylphenyl) two ring [2.2.1]-2-heptene, 8-(2,4,6-trimethylphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(o-methyl-phenyl-) two ring [2.2.1]-2-heptene, 8-(o-methyl-phenyl-) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(a methyl phenyl) two ring [2.2.1]-2-heptene, 8-(a methyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-methylphenyl) two ring [2.2.1]-2-heptene, 8-(p-methylphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,4-dimethyl phenyl) two ring [2.2.1]-2-heptene, 8-(2,4-dimethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,5-dimethyl phenyl) two ring [2.2.1]-2-heptene, 8-(2,5-dimethyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,5-dichlorophenyl) two ring [2.2.1]-2-heptene, 8-(2,5-dichlorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2,6-dichlorophenyl) two ring [2.2.1]-2-heptene, 8-(2,6-dichlorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(3,4-dichlorophenyl) two ring [2.2.1]-2-heptene, 8-(3,4-dichlorophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(adjacent iodophenyl) two ring [2.2.1]-2-heptene, 8-(adjacent iodophenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(xenyl) two ring [2.2.1]-2-heptene, 8-(xenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-sulfonic acid phenyl) two ring [2.2.1]-2-heptene, 8-(p-sulfonic acid phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the sulfonic acid chloride phenyl) two ring [2.2.1]-2-heptene, 8-(to the sulfonic acid chloride phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to carboxyl phenyl) two ring [2.2.1]-2-heptene, 8-(to carboxyl phenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5,6-diphenyl two ring [2.2.1]-2-heptene, 8,9-diphenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5,5-diphenyl two ring [2.2.1]-2-heptene, 8,8-diphenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(1-naphthyl) two ring [2.2.1]-2-heptene, 8-(1-naphthyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(2-naphthyl) two ring [2.2.1]-2-heptene, 8-(2-naphthyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(9-anthryl) two ring [2.2.1]-2-heptene, 8-(9-anthryl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(an isopropenyl phenyl)-5-methyl two ring [2.2.1]-2-heptene, 8-(an isopropenyl phenyl)-8-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the isopropenyl phenyl)-5-methyl two ring [2.2.1]-2-heptene, 8-(to the isopropenyl phenyl)-8-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(rubigan)-5-methyl two ring [2.2.1]-2-heptene, 8-(rubigan)-8-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-cyano group-5-(p-methylphenyl) two ring [2.2.1]-2-heptene, 8-cyano group-8-(p-methylphenyl) Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-methyl-5-phenyl two ring [2.2.1]-2-heptene, 9-methyl-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(p-methoxyphenyl)-6-methyl two ring [2.2.1]-2-heptene, 8-(p-methoxyphenyl)-9-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(to the hydroxyl o-methoxyphenyl)-6-methyl two ring [2.2.1]-2-heptene, 8-(to the hydroxyl o-methoxyphenyl)-9-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5-(3,4-methylene, two oxo phenyl)-6-methyl two ring [2.2.1]-2-heptene, 8-(3,4-methylene, two oxo phenyl)-9-methyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-bromo-5-phenyl two ring [2.2.1]-2-heptene, 8-phenyl-9-bromine Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-formoxyl-5-phenyl two ring [2.2.1]-2-heptene, 9-formoxyl-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-acetyl group-5-phenyl two ring [2.2.1]-2-heptene, 9-acetyl group-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-benzoyl-5-phenyl two ring [2.2.1]-2-heptene, 8-phenyl-9-benzoyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-cyano group-5-phenyl two ring [2.2.1]-2-heptene, 9-cyano group-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-nitro-5-phenyl two ring [2.2.1]-2-heptene, 9-nitro-8-phenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, Fourth Ring [8.4.1^11，14.0 ^1，10.0 ^4，9] 15-4,6,8,12-tetraene, five rings [7.6.1^11，14.1 ^1，9.0 ^10，15.0 ^5，17] 17-1,3,5,6,8,12-, six alkene, five rings [10.6.1^14，17.0 ^13，18.0 ^1，6.0 ^7，12] 19-1,3,5,7,9,11,15-, seven alkene, Fourth Ring [7.4.1^10，13.0 ^1，9.0 ^2，7] 14-2,4,6,11-tetraene, 2-oxo Fourth Ring [7.4.1^10，13.0 ^1，9.0 ^3，8] 14-3,5,7,11-tetraene, 3-oxo Fourth Ring [8.4.1^11，14.0 ^1，10.0 ^4，9] Fifteen -4,6,8,12 - four en-2 - one, 5 - phenyl-6 - carboxy-(p-methoxyphenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (a methoxy Yl-phenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (o-methoxyphenyl) bicyclo [2.2.1] -2 - Heptene, 5 - phenyl-6 - carboxy-(p-methylphenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (Room Methylphenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (o-methylphenyl) bicyclo [2.2.1] -2 - Heptene, 5 - phenyl-6 - carboxy-(p-chlorophenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (-chloroperbenzoic Phenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-(o-chlorophenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-(p-nitrophenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-(nitrophenyl Yl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-(o-nitrophenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-(p-bromophenyl) bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (bromophenyl) Bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy (o-bromophenyl) bicyclo [2.2.1] -2 - heptene, 5 - (p- Amino-phenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-aminophenyl)-6 - carboxy-ethyl- Bicyclo [2.2.1] -2 - heptene, 5 - (p-bromophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (p-bromophenyl Yl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-bromophenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (o-bromophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (o-bromophenyl) -6 - Carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (o-bromophenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - G Ene, 5 - (m-bromophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (m-bromophenyl)-6 - carboxy-methyl- Bicyclo [2.2.1] -2 - heptene, 5 - (m-bromophenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (p- Chlorophenyl) -6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (p-chlorophenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-chlorophenyl) -6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (m-chlorophenyl Yl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (m-chlorophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - Heptene, 5 - (m-chlorophenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (o-chlorophenyl) -6 - carboxylic Acid bicyclo [2.2.1] -2 - heptene, 5 - (o-chlorophenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (o-chlorophenyl) -6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-benzyl-bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-ethyl Yl bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-phenyl-bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - Carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-hydroxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (p-hydroxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-hydroxyphenyl)-6 - carboxy- Ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (o-hydroxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (o-hydroxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (o-hydroxyphenyl)-6 - carboxy- Ethyl-bicyclo [2.2.1] -2 - heptene, 5 - cyano-5 - phenyl-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - Cyano-5 - phenyl-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - cyano-5 - phenyl-6 - carboxy-ethyl- Bicyclo [2.2.1] -2 - heptene, 5 - cyano-5 - phenyl-6 - carboxy-cholesteryl bicyclo [2.2.1] -2 - heptene, 5 - (m-hydroxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (m-hydroxyphenyl)-6 - carboxy-methyl- Bicyclo [2.2.1] -2 - heptene, 5 - (m-hydroxyphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - Phenyl-6 - carboxy-allyl-bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy vinyl bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-cinnamyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-chloro-nitro Phenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (p-chloro-m-nitrophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (p-chloro-m-nitrophenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - Chloro-5 - nitrophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2 - chloro-5 - nitrophenyl)-6 - carboxy- Methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - chloro-5 - nitrophenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - Heptene, 5 - cyano-5 - (p-hydroxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - cyano-5 - (p- Hydroxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - cyano-5 - (p-hydroxyphenyl)-6 - carboxylic -Ethyl bicyclo [2.2.1] -2 - heptene, 5 - phenyl-6 - carboxy-isopropyl-bicyclo [2.2.1] -2 - heptene, 5,6 - Dibromo-5 - phenyl-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5,6 - dibromo-5 - phenyl-6 - carboxy-methyl Ring [2.2.1] -2 - heptene, 5,6 - dibromo-5 - phenyl-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,4 - Dimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3,4 - dimethoxyphenyl)-6 - carboxy- Methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,4 - dimethoxyphenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (3,5 - dimethoxy-4 - hydroxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3,5 - dimethoxy-4 - hydroxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,5 - Methoxy-4 - hydroxyphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,5 - dimethoxybenzene Yl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,5 - dimethoxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,5 - dimethoxyphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,3 - dimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,3 - dimethoxybenzene Yl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,3 - dimethoxyphenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - difluorophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - difluoro- Phenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - difluorophenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - dimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - Dimethoxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - dimethoxyphenyl) -6 - Carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - dichlorophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - G Ene, 5 - (2,4 - dichlorophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,4 - dichlorophenyl) -6 - Carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (4 - fluorophenyl) -6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (4 - fluorophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - fluorophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2 - fluorophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - fluorophenyl Yl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - fluorophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - Heptene, 5 - (3 - fluorophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - fluorophenyl) -6 - carboxy- Ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - hydroxy - 3 - methoxy-phenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - Heptene, 5 - (4 - hydroxy - 3 - methoxy-phenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - hydroxyphenyl -3 - methoxy-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - hydroxy - 4 - methoxy- Yl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - hydroxy - 4 - methoxy-phenyl)-6 - carboxy-methyl Ring [2.2.1] -2 - heptene, 5 - (3 - hydroxy - 4 - methoxy-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - G Ene, 5 - (3 - methoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - methoxyphenyl) -6 - Carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - methoxyphenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5 - (2 - methoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2 - methoxy- Yl-phenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - methoxyphenyl)-6 - carboxy-diethyl Ring [2.2.1] -2 - heptene, 5 - (4 - methoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (4 - methyl Phenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - methoxyphenyl) -6 - carboxyethyl Bicyclo [2.2.1] -2 - heptene, 5 - (3,4 - methylenedioxy-substituted phenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - G Ene, 5 - (3,4 - methylenedioxy-substituted phenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,4 - Methylenedioxy-substituted phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - methyl-phenyl) -6 - Carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (4 - methylphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - methylphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - mercapto-phenyl)-6 - carboxylic acid Ring [2.2.1] -2 - heptene, 5 - (4 - mercapto-phenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - Mercapto-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - methyl-phenyl) -6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2 - methyl-phenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - methyl Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - methylphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - methylphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - methyl Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - methyl-5 - phenyl-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - methyl-5 - phenyl-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - methyl-5 - Phenyl-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - nitrophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - nitrophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - nitrate Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - nitrophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (4 - nitrophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - nitro Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - nitrophenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2 - nitrophenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2 - nitro Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - n-octadecyl-alkoxyphenyl)-6 - carboxylic acid Bicyclo [2.2.1] -2 - heptene, 5 - (4 - n-octadecyl-alkoxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - Heptene, 5 - (4 - n-octadecyl-alkoxyphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - Hard Acyl-phenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (4 - stearoyloxy-phenyl)-6 - carboxy- Methyl-bicyclo [2.2.1] -2 - heptene, 5 - (4 - stearoyloxy-phenyl)-6 - carboxy-ethyl bicyclo [2.2.1] -2 - heptene, 5,5 - diphenyl-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5,5 - diphenyl-6 - carboxylic Methyl bicyclo [2.2.1] -2 - heptene, 5,5 - diphenyl-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,4,5 - trimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3,4,5 - trimethoxy Yl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3,4,5 - trimethoxyphenyl) -6 - carboxyethyl Bicyclo [2.2.1] -2 - heptene, 5 - (2,4,5 - trimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,4,5 - trimethoxyphenyl) -6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,4,5 - trimethoxy Yl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - (trifluoromethyl) phenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - (trifluoromethyl) phenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - Trifluoromethyl-phenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - trifluoromethoxy-phenyl) -6 - Carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (3 - trifluoromethoxyphenyl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (3 - trifluoromethoxyphenyl)-6 - carboxy-ethyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,3,4 - trimethoxyphenyl)-6 - carboxylic acid bicyclo [2.2.1] -2 - heptene, 5 - (2,3,4 - trimethoxy Yl)-6 - carboxy-methyl-bicyclo [2.2.1] -2 - heptene, 5 - (2,3,4 - trimethoxyphenyl) -6 - carboxyethyl Bicyclo [2.2.1] -2 - heptene, 5 - (4 - cyano-phenyl) bicyclo [2.2.1] -2 - heptene, 8-( 4 - cyano- Methylphenyl) tetracyclo [4.4.1 ...^2，5.1 ^7，10.0]-3-dodecylene, 5,5,6,6-tetraphenyl two ring [2.2.1]-2-heptene, 8,8,9,9-tetraphenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 6-bromo-5,5,6-triphenyl two ring [2.2.1]-2-heptene, 9-bromo-8,8,9-triphenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene, 5,5,6-triphenyl two ring [2.2.1]-2-heptene, 8,8,9-triphenyl Fourth Ring [4.4.1^2，5.1 ^7，10.0]-3-dodecylene etc.

In addition, as the norbornene monomer shown in the general formula in the above-mentioned reaction equation (II) (II-2), for example can enumerate following such norbornene monomer.

Two ring [2.2.1] hept-2-ene"s, Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-methyl-5-methoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-cyano group two ring [2.2.1] hept-2-ene"s, 8-methoxycarbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-ethoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-positive propoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-isopropoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-n-butoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl-8-methoxycarbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl-8-ethoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl-8-positive propoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl-8-isopropoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl-8-n-butoxy carbonyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 5-ethylene ring [2.2.1] hept-2-ene", 8-ethylidene Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-methyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-ethyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-propyl group Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-isopropyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, 8-normal-butyl Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-the 3-dodecylene, 5-normal-butyl two ring [2.2.1] hept-2-ene"s, 5-n-hexyl two ring [2.2.1] hept-2-ene"s, 5-cyclohexyl two ring [2.2.1] hept-2-ene"s, 5-(2-cyclohexenyl group) two ring [2.2.1] hept-2-ene"s, 5-n-octyl two ring [2.2.1] hept-2-ene"s, positive decyl two ring [2.2.1] hept-2-ene"s of 5-, 5-isopropyl two ring [2.2.1] hept-2-ene"s, 5-cyclohexenyl group two ring [2.2.1] hept-2-ene"s, 5-fluorine two ring [2.2.1] hept-2-ene"s, 5,5-difluoro two ring [2.2.1] hept-2-ene"s, 5,6-difluoro two ring [2.2.1] hept-2-ene"s, 5,5,6-trifluoro two ring [2.2.1] hept-2-ene"s, 5,5,6,6-tetrafluoro two ring [2.2.1] hept-2-ene"s, 8-fluorine Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-and 3-dodecylene, 8,8-difluoro Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-3-dodecylene, bicyclopentadiene, three cyclopentadiene, Fourth Ring pentadiene, indenes-cyclopentadiene addition product (1,4-methylene-1,4,4a, 9a-tetrahydrochysene fluorenes) etc.

In addition, make method, have no particular limits, for example can be fit to adopt the method shown in the following reaction equation (III) with the norbornene monomer of such general formula (I-1) expression.

[reaction equation (III)]

[in the above-mentioned reaction equation (III), R ¹, R ², R ³, R ⁴, wave-like line c respectively with above-mentioned general formula (1) in R ¹, R ², R ³, R ⁴, wave-like line c same meaning.]

Method with such reaction equation (III) expression, make the styrene derivative shown in cyclopentadiene shown in the above-mentioned formula (III-1) and the above-mentioned formula (III-2) carry out the method for Diels-Alder reaction specifically, thus, can obtain the norbornene monomer shown in above-mentioned formula (III-3) and (III-3 ').

As the example of the styrene derivative shown in the general formula (III-2) that in above-mentioned reaction equation (III), uses, can enumerate styrene and cinnamic acid etc.Such styrene derivative in Diels-Alder reaction, plays a role as the dienophile (dienophile) of excellence, can access desired response speed in commercial production.That is, producing from the precursor (bicyclopentadiene) of cyclopentadiene under temperature (160～200 ℃) condition of cyclopentadiene, by making the reaction of above-mentioned styrene derivative and cyclopentadiene, can high productivity obtaining the norbornene monomer of purpose.The method that obtains such styrene derivative also is not particularly limited, but because the industrial product that can produce is arranged, so obtain easily, not by commercially available compound, can utilize book (the macromolecule デ- Ha Application De Block ック Ji Foundation of publication about industrial

, macromolecule association compiles,, training wind shop in 1986 etc.) in the method for record synthesize.

In addition, as such styrene derivative, can enumerate following such styrene derivative.

4-aminobenzene ethene, the 2-acetoxy-styrene, the 4-acetoxy-styrene, the β bromstyrol, the 4-t-butyl styrene, 4-cumene ethene, the 3-bromstyrol, the 4-bromstyrol, the 2-bromstyrol, 4-bromo-β, β-difluoro styrene, 4-chloro-α-Jia Jibenyixi, the 2-chlorostyrene, the 3-chlorostyrene, the 4-chlorostyrene, between 1-chloro-4-methyl-benzene, p-chloromethyl styrene, cyano methyl styrene, o-chloromethyl ethene, 2, the 6-dichlorostyrene, 4-fluoro-α-Jia Jibenyixi, 2-fluorobenzene ethene, 3-fluorobenzene ethene, 4-fluorobenzene ethene, phenyl-pentafluoride ethene, the 2-methoxy styrene, 4-ethoxybenzene ethene, to phenoxy group styrene, to vinyl benzyl alcohol, the 4-methoxy styrene, 2-methyl styrene, the 3-methyl styrene, the 4-methyl styrene, α-Jia Jibenyixi, cis-Beta-methyl styrene, the 3-nitrostyrolene, the 4-nitrostyrolene, the 4-cyano styrene, 4-n-octyl ethene, Beta-methyl styrene, 2,3,4,5,6-phenyl-pentafluoride ethene, α-(trimethylsiloxy) styrene, styrene, 2,4,6-trimethylbenzene ethene, o-methyl styrene, between methyl styrene, p-methylstyrene, 2, the 4-dimethyl styrene, 2, the 5-dimethyl styrene, 2,4,6-trimethylbenzene ethene, 2, the 5-dichlorostyrene, 2, the 6-dichlorostyrene, 3, the 4-dichlorostyrene, adjacent iodobenzene ethene, to styryl phenyl, p styrene sulfonic acid, to the styrene sulfonic acid chloride, the 4-carboxyl styrene, cis-stilbene (cis-stilbene), trans-stilbene (trans-stilbene), 1, the 1-diphenylethlene, the 1-vinyl naphthalene, the 2-vinyl naphthalene, the 9-vinyl anthracene, between di isopropenylbenzene, to di isopropenylbenzene, to the chloro-α-Jia Jibenyixi, alpha-cyano-p-methylstyrene, propenylbenzene, anethole (anethole), isoeugenol (isoeugenol), iso-safrole (isosafrole), β-bromstyrol, cinnamic acid (cinnamaldehyde), BENZYLIDENE ACETONE (benzalacetone), benzalacetophenone (benzalacetophenone), beta-cyano styrene, beta-nitrostyrene, 1, the 2-dihydronaphthalene, acenaphthylene (acenaphthylene), luxuriant and rich with fragrance, indenes, methylene benzo indenes, coumarone, the 4-amino-cinnamic acid, the 4-bromo-cinnamic acid, the 2-bromo-cinnamic acid, trans-the 3-bromo-cinnamic acid, 3, the 4-dihydroxycinnamic acid, the 4-chloro-cinnamic acid, trans-cinnamic acid, benzyl cinnamate, ethyl cinnamate, phenyl cinnamate, methyl cinnamate, trans-the 4-hydroxycinnamic acid, trans-2 hydroxy cinnamic acid 98, the alpha-cyano cinnamic acid, the alpha-cyano ethyl cinnamate, the trans-cinnamic acid cholesteryl ester, trans-the 3-hydroxycinnamic acid, the cinnamic acid allyl ester, the cinnamic acid vinyl esters, styracine, the 2-chloro-cinnamic acid, the 3-chloro-cinnamic acid, 4-chloro-3-nitrocinnamic, 2-chloro-5-nitrocinnamic, 4-chloro-cinnamic acid methyl esters, alpha-cyano-4-hydroxycinnamic acid, Isopropyl cinnamate, α, the beta-2-dibrom ethyl cinnamate, 3, the 4-dimethoxy-cinnamic acid, 3,5-dimethoxy-4 '-hydroxycinnamic acid, 3, the 4-dimethoxy-cinnamic acid, 2, the 5-dimethoxy-cinnamic acid, trans-2, the 3-dimethoxy-cinnamic acid, 2, the 4-cinnamic acid difluoride, 2, the 4-dimethoxy-cinnamic acid, trans-2, the 4-dichloro-cinnamic acid, α, the beta-2-dibrom cinnamic acid, 3,5-dimethoxy-4 '-hydroxycinnamic acid, the 4-fluoro cinnamic acid, the 2-fluoro cinnamic acid, the 3-fluoro cinnamic acid, cinnamic acid, trans-4-hydroxyl-3-methoxy cinnamic acid, 3-hydroxyl-4-methoxy cinnamic acid, the 4-hydroxycinnamic acid, the 3-methoxy cinnamic acid, trans-the 2-methoxy cinnamic acid, the 4-methoxy cinnamic acid, 3,4-methylene dioxo cinnamic acid, the 4-methyl cinnamic acid, cis-2-methoxy cinnamic acid, the 4-mercapto-cinnamic acid, 4-methoxy cinnamic acid-2-Octyl Nitrite, the 4-octyl methoxycinnamate, 4-methoxy cinnamic acid ethyl ester, the 2-methyl cinnamic acid, the 3-methyl cinnamic acid, α-Jia Jirouguisuan, the 3-nitrocinnamic, the 4-nitrocinnamic, the 2-nitrocinnamic, the 4-ethyl nitrocinnamate, 4-n-octadecane oxygen base cinnamic acid, 4-stearoyl-oxy cinnamic acid, α-Ben Jirouguisuan, 3,4, the 5-trimethoxy cinnamic acid, 2,4, the 5-trimethoxy cinnamic acid, 3-(trifluoromethyl) cinnamic acid, 3-(trifluoromethoxy) cinnamic acid, 2,3, the 4-trimethoxy cinnamic acid, cumarin (coumarin), the vinyl benzyl prussiate, tetraphenyl ethene, 2-bromo-1,1,2-triphenyl ethene, triphenyl ethene etc.

In addition, in the norbornene monomer that obtains in the method shown in the above-mentioned employing reaction equation (III), the steric isomer at the position that is connected with two ring structures as aromatic structure exists exo isomer and endo isomer.And the exo isomer of such norbornene monomer gives " negative A " to the norborene class ring-opening polymerization polymer that obtains, and on the other hand, endo isomer gives " positive A " to the norborene class ring-opening polymerization polymer that obtains.Therefore, in phase retardation film of the present invention, according to the optical characteristics of purpose, the ratio of these isomeride that contain in the suitable selective membrane.For example, by the ratio that contains of suitable these isomeride of change, can access birefringent film does not take place in fact.In addition, so-called here positive A refers to when monadic stretching membrane, from the big character of refractive index of the variations in refractive index refractive index ratio that obtain, bearing of trend of the generation direction vertical with bearing of trend.In addition, what negative A said is the character that satisfies the condition of above-mentioned relation formula (1), refers to the little character of refractive index of the refractive index ratio of the bearing of trend direction vertical with bearing of trend.In addition, such isomeride, the reaction conditions when for example making by suitable Request for Change system, can change the ratio in the product easily, in addition, even after making monomer, also can easily change its ratio by implementing thermal treatment, this heat treated condition of change.

In addition, the method as making the norbornene monomer shown in the above-mentioned general formula (I-1) or (II-1) for example can suitably adopt the method shown in the following reaction equation (IV).

[reaction equation (IV)]

[in the reaction equation (IV), the same meaning of the n in n and the above-mentioned general formula (1), X represents chlorine atom, bromine atoms or iodine atom.]

Method with such reaction equation (IV) expression, be to utilize reductibility Heck reaction to make the benzene halide derivatives reaction shown in norbornadiene derivant shown in the general formula (IV-1) and the general formula (IV-2), obtain the method for the norbornene monomer shown in the general formula (IV-3).Utilize such reaction, the spatial configuration that can obtain the phenyl ring in the general formula (IV-3) becomes the norbornene monomer of external form coordination.

In addition, the n value in the above-mentioned reaction equation (IV) is 0 o'clock (during a norbornadiene), and the spatial configuration that is merely able to obtain phenyl ring becomes the norbornene monomer of external form.On the other hand, the n value in the above-mentioned reaction equation (IV) be 1 o'clock (be Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3 are during 8-12 carbon diene), same in the time of can be with n=0, the relative norborene ring of the spatial configuration of phenyl ring becomes exo configuration, but the steric isomer at norborene ring position connected to one another exists exo isomer and 2 kinds of isomeride of endo isomer.Such isomeride, the reaction conditions when for example creating norbornadiene derivant shown in the above-mentioned general formula (IV-1) of raw material by suitable change can easily change it and contain ratio.In addition,, also can handle, change the condition that this isomerization is handled, change the ratio that contains of above-mentioned isomeride by implementing isomerization even after making the norbornene monomer shown in the general formula (IV-3).

In addition, the catalyzer that the ring-opening polymerization of using in the reaction that makes such norbornene monomer ring-opening polymerization (reaction of the reaction of record or record in reaction equation (II) in reaction equation (I)) is used, be not particularly limited, for example can use (K.J.IVIN at Olefin Metathesis andMetathesis Polymerization, J.C.MOL, Academic Press 1997) middle double decomposition (metathesis) polymerization catalyst of putting down in writing.Promptly, can enumerate by (a) be selected from the compound that contains W, Mo, Re, V and Ti at least a kind, be the compound that contains elements such as Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al, Si, Sn, Pb (b), be selected from least a kind the catalyzer that constitutes in the compound with at least 1 this element-carbon bond or this element-hydrogen bond.Using such catalyzer, when above-mentioned ring-opening polymerization is carried out,, also can add adjuvant described later (c) in order to improve activity of such catalysts.In addition, as other catalyzer, can enumerate the metathesis catalyst that (d) is made of periodic table the 4th family～8 group 4 transition metals-Cabbeen coordination compound that does not use promotor and becket butane coordination compound etc.In addition, above-mentioned (a) composition as the representative example of the compound that contains suitable W, Mo, Re, V or Ti, can be enumerated WCl ₆, MoCl ₅, ReOCl ₃, VOCl ₃, TiCl ₄Deng.In addition, the object lesson of the compound that uses as (b) composition can be enumerated n-C ₄H ₉Li, (C ₂H ₅) ₃Al, (C ₂H ₅) ₂AlCl, (C ₂H ₅) _1.5AlCl _1.5, (C ₂H ₅) AlCl ₂, compound such as MAO, LiH etc.As the representative example of the adjuvant of (c) composition, can use alcohols, aldehydes, ketone, amine etc.In addition, as the representative example of (d) composition, can enumerate W (=N-2,6-C ₆H ₃IPr ₂) (=CHtBu) (OtBu) ₂, Mo (=N-2,6-C ₆H ₃IPr ₂) (=CHtBu) (OtBu) ₂, Ru (=CHCH=CPh ₂) (PPh ₃) ₂Cl ₂, Ru (=CHPh) (PC ₆H ₁₁) ₂Cl ₂(Grubbs I (first generation) catalyzer), Grubbs II (second generation) catalyzer, Hoveyda-Grubbs catalyzer (first generation and the second generation) etc.

Use amount as such metathesis catalyst, the ratio of mentioned component (a) and above-mentioned norbornene monomer total amount is (in reaction equation (I), the ratio that is called the norbornene monomer shown in mentioned component (a) and the above-mentioned formula (I-1), in reaction equation (II), the ratio that is called the norbornene monomer total amount shown in mentioned component (a) and above-mentioned formula (II-1) and (II-2)), be preferably 1: 500～1: 500000 scope, more preferably 1: 1000～1: 100000 scope in mol ratio " (a) composition: norbornene monomer total amount ".In addition, as (a) composition and (b) components in proportions, be preferably 1: 1～1: 100 scope, more preferably 1: 2～1: 50 scope in metallic atom ratio " (a) composition: (b) composition ".As (a) composition and (c) components in proportions, be preferably 0.005: 1～15: 1 scope, more preferably 0.05: 1～10: 1 scope with molar ratio computing " (c) composition: (a) composition ".In addition, use amount as catalyzer (d), (d) ratio of composition and above-mentioned norbornene monomer total amount is (in above-mentioned reaction equation (I), the ratio that is called the norbornene monomer total amount shown in above-mentioned (d) composition and the formula (I-1), in above-mentioned reaction equation (II), the ratio that is called the norbornene monomer total amount shown in above-mentioned (d) composition and (II-1) and (II-2)), be preferably 1: 30～1: 100000 scope, more preferably 1: 50～1: 50000 scope in mol ratio " (d) composition: norbornene monomer total amount ".

In addition, in the reaction that makes above-mentioned norbornene monomer ring-opening polymerization (reaction of the reaction of record or record in reaction equation (II) in reaction equation (I)), the method of the molecular weight of the norborene class ring-opening polymerization polymer that adjusting obtains, be not particularly limited, for example can adopt the method for suitably regulating molecular weight by change polymerization temperature, catalyst type, solvent species etc.And, as the method for such adjusting molecular weight, can suitably adopt the method that in reaction system, makes the molecular weight regulator coexistence.As the suitable molecular weight regulator of such molecular weight regulator, for example can enumerate alpha-olefines and styrene such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, wherein, preferred especially 1-butylene, 1-hexene.These molecular weight regulators can use separately or mix more than 2 kinds and use.As the use amount of such molecular weight regulator, be preferably 0.005～1.0 mole, 0.02～0.5 mole scope more preferably with respect to 1 mole of above-mentioned norbornene monomer.

In addition, as operable solvent in the reaction that makes above-mentioned norbornene monomer ring-opening polymerization (reaction of the reaction of record or record in reaction equation (II) in reaction equation (I)), preferably can dissolve the solvent of above-mentioned norbornene monomer, metathesis catalyst and molecular weight regulator, for example can enumerate paraffinics such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, naphthalane, norbornane; Aromatic hydrocarbons such as benzene,toluene,xylene, ethylbenzene, cumene; Halogenation alkanes such as chlorobutane, bromohexane, methylene chloride, ethylene dichloride, hexa-methylene dibromide, chlorobenzene, chloroform, zellon; Compounds such as aryl; Saturated carboxylic acid ester classes such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, dimethoxy-ethane, gamma-butyrolacton; Ethers such as butyl oxide, tetrahydrofuran, dimethoxy-ethane, wherein optimization aromatic hydrocarbon.These solvents can use separately or mix more than 2 kinds and use.As the use amount of such solvent, " solvent: norbornene monomer " is preferably 1: 1～30: 1 amount by quality ratio, more preferably 1: 1～20: 1 amount.

In addition, the norborene class ring-opening polymerization polymer that under the ring-opening polymerization state, obtains as mentioned above, when adopting above-mentioned reaction equation (I), it is the norborene class ring-opening polymerization polymer that contains the structural unit shown in the formula (I-2), in addition, when adopting above-mentioned reaction equation (II), be the norborene class ring-opening polymerization polymer that contains the structural unit shown in formula (II-3) and (II-4).In addition, the norborene class ring-opening polymerization polymer so that such operation obtains has ethenylidene in its structural unit.Such norborene class ring-opening polymerization polymer, can be used in to former state in the phase retardation film of the present invention of various uses, but the viewpoint that improves from the heat-resistant stability that makes the phase retardation film that obtains, preferably represent ground as above-mentioned reaction equation (I) with (II), part or all ethenylidene to norborene class ring-opening polymerization polymer carries out hydrogenation, make it to become the norborene class ring-opening polymerization polymer of the structural unit shown in the hydride (formula (I-2 ')) that contains ethenylidene and be converted into vinyl, or contain the norborene class ring-opening polymerization polymer of the structural unit shown in (II-3 ') and (II-4 ').In addition, such hydride, the aromatic rings of the side chain in the structural unit shown in above-mentioned formula (I-2 ') or (II-3 ') is not hydrogenated in fact.In addition, the hydrogenation ratio to above-mentioned ethenylidene be preferably more than 90%, more preferably 95% with, be preferably more than 98% especially.Hydrogenation ratio to ethenylidene is high more, and the thermotolerance of the norborene class ring-opening polymerization polymer that obtains just more improves, and the tendency that can fully suppress the painted and deterioration that causes because of heat is arranged.

In addition, the norborene class ring-opening polymerization polymer that contains the structural unit shown in the above-mentioned general formula (I-2) or the norborene class ring opening copolymer thing that contains the structural unit shown in above-mentioned general formula (II-3) and (II-4) are carried out the reaction of hydrogenation, have no particular limits, but as mentioned above, be necessary to carry out under the condition that the aromatic rings at side chain is not hydrogenated in fact, usually to the solution of the norborene class ring-opening polymerization polymer that contains the structural unit shown in the above-mentioned general formula (I-2) or contain in the solution of norborene class ring opening copolymer thing of the structural unit shown in above-mentioned general formula (II-3) and (II-4) and add hydrogenation catalyst, at 0～200 ℃, under preferred 20～180 ℃, make normal pressure～30MPa, the hydrogen of preferred 3～20MPa acts on it and carries out.

In addition,, can use employed catalyzer in the hydrogenation of common alkene compound, can use the heterogeneous system catalyzer, also can use the homogeneous system catalyzer as the hydrogenation catalyst that in such hydrogenation, uses.As the object lesson of such heterogeneous system catalyzer, can enumerate that noble metal catalyst materials such as making palladium, platinum, nickel, rhodium, ruthenium carries on the carriers such as being held in carbon, silicon dioxide, aluminium oxide, titania and the solid catalyst that obtains.In addition, as the object lesson of homogeneous system catalyzer, can enumerate nickel naphthenate/aluminium triethyl, acetopyruvic acid nickel/aluminium triethyl, octenoic acid cobalt/n-BuLi, cyclopentadienyl titanium dichloride/diethyl aluminum monochloride, acetic acid rhodium, chlorine three (triphenylphosphine) rhodium, dichloro three (triphenylphosphine) ruthenium, chlorine hydrogenized carbonyl three (triphenylphosphine) ruthenium, dichloro carbonyl three (triphenylphosphine) ruthenium etc.Such hydrogenation catalyst form can be Powdered, also can be granular.

Such hydrogenation catalyst, for the side chain aromatic rings in the norborene class ring-opening polymerization polymer that contains the structural unit shown in the above-mentioned formula (I-2) or the norborene class ring opening copolymer thing that contains the structural unit shown in above-mentioned formula (II-3) and (II-4) is not hydrogenated in fact, must adjust its addition, be 1: 1 * 10 in weight ratio " ring-opening polymerization polymer: hydrogenation catalyst " preferably ^-6～1: 2 ratio is used.

In addition, phase retardation film of the present invention is to stretch film that the norborene class ring-opening polymerization polymer related to by the invention described above constitutes and the film that forms.The method of the film that manufacturing is made of such norborene class ring-opening polymerization polymer is not particularly limited, and can suitably adopt known method.In addition, when making such film, in the scope that does not exceed purport of the present invention, promptly in the scope of the optical characteristics that does not hinder phase retardation film of the present invention, can add other macromolecule, surfactant, polyelectrolyte, electric conductivity coordination compound, silicon dioxide, aluminium oxide, dye material, thermal stabilizer, ultraviolet light absorber, antistatic agent, antiblocking agent, lubricant, plastifier, wet goods.In addition,, also be not particularly limited, can suitably adopt existing known drawing process making above-mentioned norborene class ring-opening polymerization polymer form the method that stretches behind the film.

In addition, be used to make the method that is fit to of the film of such norborene class ring-opening polymerization polymer, for example can enumerate public methods such as casting method (solution casting method), extrusion by melting, rolling process, compression forming method.In addition, as the building mortion that uses in such casting method, can use dry type casting machine, band casting machine, spin coater etc.In addition, as extrusion by melting, can enumerate T die head method and blow moulding.

In addition, as the object lesson of the solvent that in above-mentioned casting method, uses, for example can enumerate ring-type ketones such as cyclohexanone, cyclopentanone; Lactone such as gamma-butyrolacton, δ-Wu Neizhi; Aromatic hydrocarbons such as benzene,toluene,xylene, ethylbenzene, cumene; Halogenation alkanes such as methylene chloride, ethylene dichloride, chlorobenzene, dichloro-benzenes, chloroform, zellon; Ethers, N-Methyl pyrrolidone, N such as compounds such as aryl, butyl oxide, tetrahydrofuran, dimethoxy-ethane, dinethylformamide, N, N-dimethyl acetamide, dimethyl sulfoxide (DMSO) isopolarity solvent, wherein optimization aromatic hydrocarbon, halogenation alkane, aryl class.In addition, these solvents can use separately or mix more than 2 kinds and use.

In addition, make above-mentioned norborene class ring-opening polymerization polymer form the method that stretches behind the film, tentering method, Guan Fa etc. can be enumerated as biaxial stretch-formed method, tank pulling method, radiation pulling method, hot blast heating, hot plate heating, roller heating etc. can be enumerated as the uniaxial tension method.

As the thickness of the phase retardation film of the present invention that obtains of operation, be not particularly limited, but wish it is 10～500 μ m, be more preferably 30～200 μ m.Phase retardation film thickness is during less than 10 μ m, and mechanical property is arranged and add the tendency that the operability in man-hour descends for 2 times, in addition, and greater than 500 μ m the time, the tendency that has pliability to have problems.In addition, the stretching ratio when obtaining phase retardation film of the present invention also is not particularly limited, but preferably about 1.1～5.0 times.

The phase difference value of phase retardation film of the present invention is the scope of 5～2000nm, it is the scope that to select according to purpose, when using as 1/2 λ plate, phase differential in the visible light of wavelength 550nm wishes it is 200～400nm, when using as 1/4 λ plate, the phase differential in the visible light of wavelength 550nm wishes it is 90～200nm.

In addition, in phase retardation film of the present invention, the purpose for giving functions such as gas barrier property, mar resistance, resistance to chemical reagents, anti-dazzle property can also possess film.Form the method for such film; for example at various thermoplastic resins; has amino; imino group; epoxy radicals; the thermoset resin of silicyl etc.; has acryloyl group; methacryl; add polymerization inhibitor in the radiation-curing type resin of vinyl etc. or the potpourri of these resins; the wax class; spreading agent; dye material; solvent; plastifier; ultraviolet light absorber; inorganic fillers etc. can be adopted the gravure roll coated method of utilizing; Meyer rod cladding process; contrary roller cladding process; the immersion coating method; the air knife knife coating; the roll coated method; the extrusion coated method; the contact cladding process; the blowing cladding process; the spray coating method; methods such as spin coating method are with the method for its coating.These films can also be after coating, as required, be cured or carried out heat curing by heating by radioactive ray, makes the cured film layer.In addition, under the situation of when forming such film, printing, can use the method for photogravure mode, transfer printing mode, deflection mode, silk screen process mode etc.In addition, in phase retardation film of the present invention, for giving purposes such as gas tightness, can also possess with aluminium, silicon, magnesium, zinc etc. is the metal oxide layer of principal ingredient.Such metal oxide layer is formed by vacuum vapour deposition, metallikon, ion plating method, plasma CVD method etc.

In addition, also can make phase retardation film of the present invention and other film laminationization.As the method that makes phase retardation film of the present invention and other film laminationization like this, can suitably adopt existing known method, for example can enumerate lamination process methods such as thermal bonding methods such as heat sealing method, dash current Sealing Method, ultrasound wave bonding method, high frequency bonding method, extruding layer platen press, hot melt layer platen press, dry pressing, wetpressing, solvent-free bonding coat platen press, lamination methods, coetrusion etc.In addition, by the film of laminationization, for example can enumerate polyester resin film, polyvinyl alcohol ester resin film, cellulosic resin film, polyfluoroethylene resin film, polyvinylidene chloride resin film, polyacrylonitrile resin film, nylon-based resin film, polythylene resin film, polypropylene resin film, acetate resins film, polyimide resin film, polycarbonate resin adipose membrane, polyacrylate resin film etc.

Then, liquid crystal indicator of the present invention is described.That is, liquid crystal indicator of the present invention is characterised in that the phase retardation film that possesses the invention described above.

The phase retardation film of the invention described above is to have high transparent and excellent wavelength dispersibility; can give the phase retardation film of given reference phase difference to the light of wide region; very high with the adaptation of other material; even in negative birefringence, also can reach optical characteristics as special negative A; and can reach birefringent wavelength dispersion characteristic is become against disperseing, therefore as 1/4 λ plate in the reflection-type liquid-crystal display device; 1/2 λ plate in the liquid crystal projection apparatus and 1/4 λ plate; 1/2 λ plate in the transmission type liquid crystal display device and 1/4 λ plate; the diaphragm of the light polarizing film of in liquid crystal indicator, using; antireflection films etc. are useful.

Therefore, liquid crystal indicator of the present invention can possess the phase retardation film of the invention described above as 1/2 λ plate, 1/4 λ plate, diaphragm, antireflection film etc., and other structure can be same with existing known liquid crystal indicator.

In addition, phase retardation film of the present invention forms film with ceramic membranes such as indium tin oxide and indium-zinc oxides by the plasma process that uses DC or glow discharge on its face, also can use as the ELD in touch-screen and the liquid crystal indicator etc.

Embodiment

Below, based on embodiment and comparative example, be described more specifically the present invention, but the present invention is not limited to following embodiment.

The evaluating characteristics of polymkeric substance that obtains in each synthesis example and the phase retardation film that obtains in each embodiment at first is described.

＜glass transition temperature: Tg 〉

(Perkin-Elmer society produces, trade name: DSC7), establishing programming rate is 20 ℃ of per minutes, flows down the mensuration of the glass transition temperature that carries out the polymkeric substance that obtains in each synthesis example at nitrogen to use differential scanning calorimeter.

＜molecular weight and molecular weight distribution 〉

As determinator, (GPC, Tosoh Co., Ltd. produce, trade name: HLC-8020/4 root post: Tosoh Co., Ltd. produces, trade name: TSK gelGMHHR) to use gel permeation chromatography, solvent uses tetrahydrofuran (THF), obtains weight-average molecular weight (Mw), the molecular weight distribution (Mw/Mn) of the polystyrene conversion of the polymkeric substance that obtains in each synthesis example.In addition, Mn represents number-average molecular weight.

＜monomer and polymer molecular structure 〉

(NMR, VARIAN society produce, trade name: UNITY INOVA-600), be determined at the polymkeric substance that obtains in each synthesis example in the deuterate chloroform to use superconduction nuclear magnetic resonance absorption plant ¹H-NMR, ¹³C-NMR.From the data that obtain carry out the interior type of monomer/external form than and the hydrogenation ratio of polymkeric substance (contain the X the norborene class ring-opening polymerization polymer of the structural unit shown in the above-mentioned general formula (1) ¹Or contain X in the norborene class ring opening copolymer thing of the structural unit shown in above-mentioned general formula (2) and (3) ¹And X ²Be transformed to formula-CH ₂CH ₂-shown in the ratio of base) calculating and the evaluation of molecular structure.

＜phase differential, birefringence evaluation, birefringent wavelength dispersion value are estimated 〉

Use to postpone analyzer (prince's instrumentation society produces, trade name: KOBRA21DH) phase retardation film to obtaining at each embodiment and comparative example, measure delay (Re) and birefringent wavelength dispersion value (D) by the following formula definition.

Re＝(nx-ny)×d

Nx: the refractive index of draw direction

Ny: the refractive index of the direction vertical with draw direction

D: the thickness of film (nm)

D: birefringent wavelength dispersion value Δ n (λ=481nm)/Δ n (λ=589nm).

(synthesis example 1)

＜norbornene monomer (monomer) A, B's is synthetic 〉

In the autoclave of 2L, drop into 4-t-butyl styrene (856g, 5.36mol), bicyclopentadiene (709g, 5.36mol), 4-tert-butyl catechol (44.6g, 0.27mol), toluene (200mol), 185 ℃ of following heated and stirred 4 hours.Initial reaction stage shows the pressure of 0.4MPa, along with effluxion, pressure reduce, finally shows 0.2MPa.Then, stop the heating after, put naturally cold, drop to room temperature after, open the high pressure kettle cover, the taking-up reactant.

Then, the reactant that the refining operation like this of distillation obtains is obtained the fraction A of 118～120 ℃/1mmHg and the fraction B of 165～170 ℃/1mmHg.The output of fraction A is that the output of 640g (productive rate 53%, be benchmark with the t-butyl styrene), fraction B is 97g (productive rate 6%, be benchmark with the t-butyl styrene).The gas chromatographic analysis and the NMR that carry out fraction A analyze, and its results verification is that interior type (endo)/external form (exo) is 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene (following general formula (4)) of 79/21 than (isomer ratio).

[fraction A]

In addition, fraction B is also carried out gas chromatographic analysis and NMR analyze, its results verification is that interior type-Nei type (endo-endo)/interior type-external form (endo-exo) is than 8-(to the tert-butyl-phenyl) Fourth Ring [4.4.1 that is 87/13 ^2,5.1 ^7,10.0]-3-dodecylene (following general formula (5)).

[fraction B]

Then, heating for dissolving 300g fraction A in 1200ml methyl alcohol is put coldly naturally, just obtains the crystallization of 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene (A) of 165g.The purity of the crystallization that obtains is 98%, and interior type (endo)/external form (exo) is than being 80/20.In addition, heating for dissolving 30g fraction B in the 150ml isopropyl alcohol is put coldly naturally, just obtains 8-(to the tert-butyl-phenyl) Fourth Ring [4.4.1 of 18g ^2,5.1 ^7,10.0]-crystallization of 3-dodecylene (B).The purity of the crystallization that obtains is 99%, and interior type-Nei type (endo-endo)/interior type-external form (endo-exo) is than being 100/0.

The polymerization of＜norbornene monomer A 〉

Under blanket of nitrogen,, at room temperature stirred 20 hours than the anhydrous toluene solution (2ml) that is interpolation 1-hexene (2.5 μ l, 0.2mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%) in the anhydrous toluene solution (20ml) of 80/20 5-(to tert-butyl-phenyl), two ring [2.2.1]-2-heptene (A) (2.26g, 0.01mol) in interior type/external form.Then,, put in the 3000ml methyl alcohol, filter the precipitation that obtains with the polymer fluid of 100ml dilution with toluene thickness.Then, drying precipitated by vacuum drier, obtain ring-opening polymerization polymer (pA) 1.90g (productive rate 85%) of A.The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 90000, Mw/Mn is 1.6.

The polymerization of＜norbornene monomer B 〉

Under blanket of nitrogen, interior type-Nei type/interior type-external form than 8-(to the tert-butyl-phenyl) Fourth Ring [4.4.1 that is 100/0 ^2,5.1 ^7,10.0]-and add the anhydrous toluene solution (2ml) of 1-hexene (2.5 μ l, 0.2mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%) in the anhydrous toluene solution (20ml) of 3-dodecylene (B) (2.90g, 0.01mol), at room temperature stirred 20 hours.Then,, put in the 3000ml methyl alcohol, filter the precipitation that obtains with the polymer fluid of 100ml dilution with toluene thickness.Then, drying precipitated by vacuum drier, obtain ring-opening polymerization polymer (pB) 2.84g (productive rate 98%) of B.The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 125000, Mw/Mn is 1.5.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer A (pA) 〉

Ring-opening polymerization polymer (pA) 1.9g, dimethylbenzene (150ml), RuHCl (the CO) (PPh that in the autoclave of capacity 0.2L, add 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene ₃) ₃(19mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, inject the reaction solution that such operation obtains in 3000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (HpA) 1.69g (productive rate 89%) that 5-(to tert-butyl-phenyl) two encircles the ring-opening polymerization polymer of [2.2.1]-2-heptene.

The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 97000, Mw/Mn is 1.5.In addition, to the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 1.On the other hand, use DSC to measure Tg, its as a result Tg be 118 ℃.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer B (pB) 〉

In the autoclave of capacity 0.2L, add 8-(to tert-butyl-phenyl) Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-ring-opening polymerization polymer (pB) 2.0g of 3-dodecylene, dimethylbenzene (150ml), RuHCI (CO) (PPh ₃) ₃(20mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, inject this reaction solution in 3000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains 8-(to tert-butyl-phenyl) Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-hydride (HpB) 1.99g (productive rate 99.5%) of the ring-opening polymerization polymer of 3-dodecylene.

The product that such operation obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 96400, Mw/Mn is 1.5.In addition, to the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 2.On the other hand, use DSC to measure Tg, its as a result Tg be 226 ℃.

(synthesis example 2)

＜interior type/external form is more synthetic than different norbornene monomer C, D's 〉

After in the glass straight tube of about 10cm (quartzy system), filling in silica wool, be heated to about 340～380 ℃, under the vacuum condition, use addition funnel Dropwise 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene (interior type/external form=79/21), carry out thermal decomposition.Resultant of reaction is the high 5-(to tert-butyl-phenyl) of t-butyl styrene, cyclopentadiene and outer body content two ring [2.2.1]-2-heptene.This is because of interior type body heat instability, if improve the just cause of raising of heat decomposition temperature, outer body content.In addition, when temperature rises, the productive rate of 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene descends.The result of the thermal decomposition under 340 ℃ of heat decomposition temperatures is to obtain interior type/external form than 5-(to tert-butyl-phenyl) two ring [the 2.2.1]-2-heptene (C) that are 50/50 with productive rate 50%.In addition, if heat decomposition temperature is brought up to 380 ℃, just obtain interior type/external form than 5-(to tert-butyl-phenyl) two ring [the 2.2.1]-2-heptene (D) that are 24/76 with productive rate 13%.

The polymerization of＜norbornene monomer C 〉

Under blanket of nitrogen,, at room temperature stirred 20 hours than the anhydrous toluene solution (2ml) that is interpolation 1-hexene (2.5 μ l, 0.2mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%) in the anhydrous toluene solution (20ml) of 50/50 5-(to tert-butyl-phenyl), two ring [2.2.1]-2-heptene (C) (2.26g, 0.01mol) in interior type/external form.Then,, put in the 3000ml methyl alcohol, filter the precipitation that obtains with the polymer fluid of 100ml dilution with toluene thickness.Then, drying precipitated by vacuum drier, obtain ring-opening polymerization polymer (pC) 2.19g (productive rate 97%) of C.The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 113000, Mw/Mn is 1.4.

The polymerization of＜norbornene monomer D 〉

Under blanket of nitrogen,, at room temperature stirred 20 hours than the anhydrous toluene solution (2ml) that is interpolation 1-hexene (2.5 μ l, 0.2mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%) in the anhydrous toluene solution (20ml) of 24/76 5-(to tert-butyl-phenyl), two ring [2.2.1]-2-heptene (D) (2.26g, 0.01mol) in interior type/external form.Then,, put in the 3000ml methyl alcohol, filter the precipitation that obtains with the polymer fluid of 100ml dilution with toluene thickness.Then, drying precipitated by vacuum drier, obtain ring-opening polymerization polymer (pD) 1.74g (productive rate 77%) of D.The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 129000, Mw/Mn is 1.7.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer C (pC) 〉

Type/external form is encircled ring-opening polymerization polymer (pC) 2.0g, dimethylbenzene (150ml), RuHCl (the CO) (PPh of [2.2.1]-2-heptene in adding in the autoclave of capacity 0.2L than the 5-(to tert-butyl-phenyl) two that is 50/50 ₃) ₃(20mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, in 3000ml methyl alcohol, inject this reaction solution, separate to reclaim precipitation, the precipitation that drying obtains obtains interior type/external form than the 5-(to tert-butyl-phenyl) two that is 50/50 and encircles hydride (HpC) 1.96g (productive rate 98%) of the ring-opening polymerization polymer of [2.2.1]-2-heptene.

The product that such operation obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 112000, Mw/Mn is 1.5.To the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 3.On the other hand, use DSC to measure Tg, its as a result Tg be 107 ℃.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer D (pD) 〉

Type/external form is encircled ring-opening polymerization polymer (pD) 2.0g, dimethylbenzene (150ml), RuHCl (the CO) (PPh of [2.2.1]-2-heptene in adding in the autoclave of capacity 0.2L than the 5-(to tert-butyl-phenyl) two that is 24/76 ₃) ₃(20mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, in 3000ml methyl alcohol, inject this reaction solution, separate to reclaim precipitation, the precipitation that drying obtains obtains interior type/external form than the 5-(to tert-butyl-phenyl) two that is 24/76 and encircles hydride (HpD) 1.70g (productive rate 85%) of the ring-opening polymerization polymer of [2.2.1]-2-heptene.

The product that such operation obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 117000, Mw/Mn is 1.5.In addition, to the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 4.On the other hand, use DSC to measure Tg, its as a result Tg be 105 ℃.

(synthesis example 3)

＜external form norbornene monomer E's is synthetic 〉

According at Angew.Chem.Int.Ed., 39, p1946 (distribution in 2000) and ibid., 34, the method for record among the p1844 (nineteen ninety-five distribution), carry out synthesizing of external form norbornene monomer E.At first in the there-necked flask of 0.3L, drop into 4-tert-butyl group iodobenzene (5g, 19.22mmol), two norbornadienes (5.66g, 61.50mmol), trans-two (μ-acetonato) two [neighbour-(two-o-tolyl phosphino-) benzyl] two palladiums (II) (90mg, 0.5mol%), DMSO (82ml), NEt ₃(6.22g, 61.5mmol), formic acid (2.26g, 49.2mmol) were 120 ℃ of following heated and stirred 16 hours.Then, behind the reaction solution that obtains of cooling, inject the frozen water of 300ml, use separating funnel to extract with normal hexane (50ml * 3 time).After this, behind the clean hexane solution of saturated aqueous common salt, carry out drying, filter extract, concentrate, obtain the thick product of 3.62g thus with anhydrous magnesium sulfate.Then, the thick product that obtains is made with extra care in distillation, obtains the cut E of 104 ℃/1mmHg.The output of cut E is 2.45g (productive rate 55%).The gas chromatographic analysis and the NMR that carry out cut E analyze, and type/external form is 5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene of 0/100 than (isomer ratio) in its results verification.

The polymerization of＜norbornene monomer E 〉

Under blanket of nitrogen,, at room temperature stirred 20 hours than the anhydrous toluene solution (2ml) that is interpolation 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.7mg, 0.05mol%) in the anhydrous toluene solution (23ml) of 0/100 5-(to tert-butyl-phenyl), two ring [2.2.1]-2-heptene (E) (2.61g, 11.6mmol) in interior type/external form.Then,, put in the 3000ml methyl alcohol, filter the precipitation that obtains with the polymer fluid of 200ml dilution with toluene thickness.Then, drying precipitated by vacuum drier, obtain ring-opening polymerization polymer (pE) 2.28g (productive rate 87%) of E.The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 174000, Mw/Mn is 2.4.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer E (pE) 〉

Type/external form is encircled ring-opening polymerization polymer (pE) 2.3g, dimethylbenzene (150ml), RuHCl (the CO) (PPh of [2.2.1]-2-heptene in adding in the autoclave of capacity 0.2L than the 5-(to tert-butyl-phenyl) two that is 0/100 ₃) ₃(23mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, in 2000ml methyl alcohol, inject this reaction solution, separate to reclaim precipitation, the precipitation that drying obtains obtains interior type/external form than the 5-(to tert-butyl-phenyl) two that is 0/100 and encircles hydride (HpE) 2.0g (productive rate 89%) of the ring-opening polymerization polymer of [2.2.1]-2-heptene.

The product that such operation obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 173900, Mw/Mn is 2.4.To the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 5.On the other hand, use DSC to measure Tg, its as a result Tg be 108 ℃.

(synthesis example 4)

＜norbornene monomer F's is synthetic 〉

(i) phenyl cinnamate is synthetic

In the there-necked flask of 1L, flow down at nitrogen and to add trans-cinnamoyl chloride (100g, 0.60mol), phenol (59.3g, 0.63mol), THF (500ml), ice-cold down, use addition funnel to drip the THF solution (100ml) of triethylamine (63.8g, 0.63mol).Dropping drops into reactant liquor after finishing afterwards, at room temperature to stir 12 hours in water-bath.The white precipitate that filtration obtains is behind the drying under reduced pressure, output is 135.5g (productive rate 99.9%).If with its heating for dissolving, cooling in about 200ml methyl alcohol, just obtain white crystals (112.6g, productive rate 83.8%).In addition, the crystallization that obtains is confirmed to be object trans-cinnamic acid phenyl ester by the NMR structure analysis.

(ii) norbornene monomer F's is synthetic

In the autoclave of capacity 0.3L, drop into trans-cinnamic acid phenyl ester (112g, 0.5mol), bicyclopentadiene (36.4g, 0.55mol), toluene (100ml) that aforesaid operations obtains, 180 ℃ of following heated and stirred 4 hours.Then, stop heating after, carry out nature put cold, drop to room temperature after, open the high pressure kettle cover, take out reactant.Then, concentrate this reactant, a part of concentrate (1.2g) is got HPLC (Japanese analytical industry production, LC-918) by the recycle branch carry out separation and purification, obtain object 5-phenyl-6-carboxyl phenyl two ring [2.2.1]-2-heptene (norbornene monomer F: 0.58g (reaction yield 40%) (the cycle index 7 times) compound shown in the following chemical formula (6))

In addition, 4 such branch extract operations obtain the 2.7g object repeatedly.The object that obtains of operation is that type in the isomer ratio/external form is than the potpourri that is 60/40 by the result of NMR structure analysis like this.

The polymerization of＜norbornene monomer F 〉

Under blanket of nitrogen,, at room temperature stirred 20 hours than the anhydrous THF solution (5ml) that is interpolation Grubbs II catalyzer (3.9mg, 0.05mol%) in the anhydrous THF solution (25ml) of 60/40 5-phenyl-6-carboxyl phenyl two ring [2.2.1]-2-heptene (F) (2.67g, 9.2mmol) in interior type/external form.Then, with the polymer fluid that the THF of 200ml dilutes thickness, put in the 3000ml methyl alcohol precipitation that filtration obtains.Then, drying precipitated by vacuum drier, obtain 5-phenyl-6-carboxyl phenyl two and encircle ring-opening polymerization polymer (pF) 2.3g (productive rate 87%) of [2.2.1]-2-heptene (F).The product that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 3096000, Mw/Mn is 2.7.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer F (pF) 〉

Ring-opening polymerization polymer (pF) 2.20g, dimethylbenzene (150ml), RuHCl (the CO) (PPh that in the autoclave of capacity 0.2L, add 5-phenyl-6-carboxyl phenyl two ring [2.2.1]-2-heptene ₃) ₃(22mg), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains is with the hydrogen release.Then, inject this reaction solution in 3000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains 5-phenyl-6-carboxyl phenyl two and encircles hydride (HpF) 1.97g (productive rate 89.5%) of the ring-opening polymerization polymer of [2.2.1]-2-heptene.

The product that such operation obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 3920000, Mw/Mn is 1.8.To the product use NMR that obtains, the hydrogenation ratio of measuring the alkene unsaturated link, be confirmed to be 99.9%.In addition, because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.The NMR figure that expression obtains in Fig. 6.On the other hand, use DSC to measure Tg, its as a result Tg be 103 ℃.

(embodiment 1～8)

Use the norborene class ring-opening polymerization polymer { HpA (embodiment 1), HpB (embodiment 2), HpC (embodiment 3), HpD (embodiment 4), HpE (embodiment 5), HpF (embodiment 6) } that in synthesis example 1～4, obtains respectively, make phase retardation film of the present invention (embodiment 1～6).Also use HpG (embodiment 7) that makes by the polymer solution potpourri of HpA (0.925g) and HpC (0.695g) and the HpH (embodiment 8) that makes by the polymer solution potpourri of HpC (0.462g) and HpD (0.420g) respectively, make phase retardation film (embodiment 7～8).That is, preparing the chlorobenzene solution that contains each polymkeric substance with 5wt% concentration at first respectively, is membranaceous, air dry 24 hours by the casting method curtain coating on glass plate.Then, after the film that obtains peeled off from glass plate respectively, use the vacuum drier that remains near temperature (Tg-10 of each polymkeric substance ℃) polymer Tg that becomes each membrane material, be dried to residual solvent concentration and become below the 1.0 weight %.The transparency of operating the film that obtains like this is all very high.The thickness of the film that obtains in addition, is 30～150 μ m.Then, the film that obtains is cut to thin oblong-shaped (size: 5.0 * 4.0cm), use biaxial stretch-formed device (production of bavin mountain science, trade name " SS-60 type "), becoming under the temperature conditions of the polymer Tg of each membrane material+10 ℃, carry out the uniaxial tension of 200% (2.0 times) with the draw speed of 50mm/min, obtain phase retardation film of the present invention (embodiment 1～8).

(evaluation of the optical characteristics of the phase retardation film that in embodiment 1～8, obtains)

By postponing the birefringence that analyzer is determined at the phase retardation film that obtains among the embodiment 1～8.The result that expression obtains in table 1.In addition, the trade name " 2010PrismCoupler " of being produced by Metricon society is measured refractive index.In addition, the draw direction of the uniaxial tension of above-mentioned film is defined as X-axis, and will be defined as Y-axis and Z axle (Y-axis and Z axle be quadrature also), measure the refractive index (Nx) of X-axis, the refractive index (Ny) of Y-axis, the refractive index (Nz) of Z axle with the direction of X-axis quadrature.

In addition, about the phase retardation film that in embodiment 1, embodiment 3～5, embodiment 7～8, obtains, the outer body ratio that the expression demonstration contains in Fig. 7 and the chart of birefringent relation.In addition, about the phase retardation film that in embodiment 1, embodiment 3～5, embodiment 7～8, obtains, outer body ratio that the expression demonstration contains in Fig. 8 and wavelength dispersion value { D=(△ n: λ 481nm)/(Δ n: the chart of } relation λ 589nm).

[table 1]

	Postpone (nm)	Nx	Ny	Nz	Thickness μ m	Wavelength dispersion value D ^*1	The ratio of the interior type/external form of monomer
	Postpone (nm)	Nx	Ny	Nz	Thickness μ m	Wavelength dispersion value D ^*1	The ratio of the interior type/external form of monomer	Embodiment 1 (HpA)	73.2	1.544	1.541	1.541	40	0.94	79/21
Embodiment 2 (HpB)	296.4	1.521	1.516	1.516	65	1.04	100/0 ^*2	Embodiment 1 (HpA)	73.2	1.544	1.541	1.541	40	0.94	79/21
Embodiment 2 (HpB)	296.4	1.521	1.516	1.516	65	1.04	100/0 ^*2	Embodiment 3 (HpC)	26.3	1.543	1.542	1.542	31	0.76	50/50
Embodiment 4 (HpD)	15.7	1.543	1.544	1.544	50	1.41	24/76	Embodiment 3 (HpC)	26.3	1.543	1.542	1.542	31	0.76	50/50
Embodiment 4 (HpD)	15.7	1.543	1.544	1.544	50	1.41	24/76	Embodiment 5 (HpE)	108.2	1.541	1.543	1.543	60	1.17	0/100
Embodiment 6 (HpF)	130.2	1.600	1.596	1.596	31	1.02	60/40	Embodiment 5 (HpE)	108.2	1.541	1.543	1.543	60	1.17	0/100
Embodiment 6 (HpF)	130.2	1.600	1.596	1.596	31	1.02	60/40	Embodiment 7 (HpG)	116.6	1.545	1.543	1.543	99	0.91	65/35
Embodiment 8 (HpH)	11.1	1.544	1.544	1.544	97	0.16	35/65	Embodiment 7 (HpG)	116.6	1.545	1.543	1.543	99	0.91	65/35

* type-Nei type/interior type-external form ratios in the 1 Δ n@481nm/ Δ n@589nm * 2

From the result shown in table 1 and Fig. 7 as can be known, confirm that the phase retardation film that obtains is a film of bringing into play function as phase retardation film well in each embodiment.Also because the phase retardation film (embodiment 4,5) of HpD and HpE satisfies the relation shown in the following formula (2), so be confirmed to be film as so-called negative A phase retardation film performance function.

Ny＝Nz>Nx (2)

In addition, from the result shown in Fig. 8 as can be known, confirm each phase retardation film birefringent wavelength dispersion value D=(Δ n: λ 481nm)/(Δ n: λ 589nm) }, according to the interior type/external form ratio of monomer and difference, about the phase retardation film that obtains among the

embodiment

1,3,7,8, confirm to become the contrary phase retardation film that disperses.

(evaluation of the adaptation of the phase retardation film that in embodiment 1～8, obtains)

On the surface of triacetyl cellulose substrate, (the synthetic production in East Asia, UVX-1620) makes the phase retardation film that obtains in embodiment 1～8 bonding with ultraviolet-curing adhesive, method according to the JIS-K5400 record, when estimating their adaptation, confirm that the adaptation of any one phase retardation film and tri acetyl cellulose membrane is all very high.

(synthesis example 5)

＜norbornene monomer I synthesizes-1 〉

Under blanket of nitrogen, in the there-necked flask of 1.0L, drop into 2-dicyclohexyl phosphino--2 '-methyl biphenyl (258mg, 0.708mmol), palladium (13.3mg, 0.059mmol), DMSO (250ml), norbornadiene (19ml, 190mmol), 4-tert-butyl group bromobenzene (10ml, 59mmol), NEt ₃(26.7ml, 192mmol) and formic acid (5.9ml, 154mmol), heated and stirred is 6 hours under 80 ℃ temperature conditions, obtains reaction solution.Then, the reaction solution that obtains is cooled to 30 ℃, be injected in the frozen water of 300ml after, use separating funnel to extract with normal hexane (50ml * 3 time), obtain hexane solution.Then, water and saturated aqueous common salt carry out drying with anhydrous magnesium sulfate after cleaning, and obtain extract.Then, filter said extracted liquid, concentrate, obtain the thick product of 13.4g.

Then, above-mentioned thick product is made with extra care in distillation, obtains the cut (product) of 104 ℃/1mmHg.The output of such product is 10.7g (productive rate 80%).In addition, carry out the result that gas chromatographic analysis and NMR analyze, confirm that the product that obtains is that interior type/external form is external form-5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene (norbornene monomer I: the compound shown in the following chemical formula (7)) of 0/100 than (isomer ratio).

(synthesis example 6)

＜norbornene monomer I synthesizes-2 〉

Under blanket of nitrogen, in the there-necked flask of 1.0L, drop into 2-(dicyclohexyl phosphino-) biphenyl (248mg, 0.708mmol), palladium (13.3mg, 0.059mmol), DMSO (250ml), norbornadiene (19ml, 190mmol), 4-tert-butyl group bromobenzene (10ml, 59mmol), NEt3 (26.7ml, 192mmol) and formic acid (5.9ml, 154mmol), 80 ℃ of following heated and stirred 8 hours, obtain reaction solution.Then, reaction solution is cooled to 30 ℃, be injected in the frozen water of 300ml after, use separating funnel to extract with normal hexane (50ml * 3 time), obtain hexane solution.Then, water and saturated aqueous common salt carry out drying with anhydrous magnesium sulfate after cleaning above-mentioned hexane solution, obtain extract.Then, filter said extracted liquid, concentrate, obtain the thick product of 13.8g.

Then, above-mentioned thick product is made with extra care in distillation, obtains the cut (product) of 104 ℃/1mmHg.The output of such product is 11.2g (productive rate 84%).Carry out the result that gas chromatographic analysis and NMR analyze, confirm that above-mentioned product is that interior type/external form is external form-5-(to tert-butyl-phenyl) two ring [2.2.1]-2-heptene (norbornene monomer I) of 0/100 than (isomer ratio).

(synthesis example 7)

＜norbornene monomer I and Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-copolymerization-1 of 3-dodecylene (norbornene monomer J) 〉

Under blanket of nitrogen, preparation contains the norbornene monomer I (1.70g, 7.5mmol) that obtains and the anhydrous toluene solution (23ml) of the norbornene monomer J (0.40g, 2.5mmol) shown in the following chemical formula (8) in synthesis example 5.

In above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) that contains 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), descend stirring 20 hours in room temperature (25 ℃), obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, by the dry above-mentioned precipitation of vacuum drier, obtain ring opening copolymer thing (pI) 1.71g (productive rate 82%) of norbornene monomer I and norbornene monomer J.The multipolymer (pI) that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 290000, Mw/Mn is 4.9.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer I and norbornene monomer J (pI) 〉

In the autoclave of capacity 0.2L, add pI (1.68g), dimethylbenzene (150ml), RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, with the reaction solution that obtains be cooled to 30 ℃, with the hydrogen release.Then, inject this reaction solution in 2000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpI)) 1.4g (productive rate 8l%) of pI.

The product (HpI) that such operation is obtained confirmed by GPC, and the weight-average molecular weight of polystyrene conversion (Mw) is 263000, Mw/Mn is 4.5.In addition, use DSC to measure Tg, its as a result Tg be 123 ℃.Also to the multipolymer (HpI) that obtains, the hydrogenation ratio that uses NMR mensuration alkene unsaturated link.The NMR figure that expression obtains in Fig. 9.From result shown in Figure 9 as can be known, in the multipolymer that obtains (HpI), confirm that the hydrogenation ratio of alkene unsaturated link is 99.9%.In addition, in the multipolymer that obtains (HpI), because do not change, so confirm that the aromatic rings of side chain is not hydrogenated in fact from the signal of aromatic rings.

(synthesis example 8)

＜norbornene monomer I and Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-copolymerization-2 of 3-dodecylene (norbornene monomer J) 〉

Under blanket of nitrogen, preparation contains the norbornene monomer I (1.13g, 5.0mmol) that obtains and the anhydrous toluene solution (23ml) of the norbornene monomer J (0.80g, 5.0mmol) shown in the above-mentioned chemical formula (8) in synthesis example 5, in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) contain 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stir 20 hours, obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, by the dry above-mentioned precipitation of vacuum drier, obtain ring opening copolymer thing (pJ) 1.70g (productive rate 88%) of norbornene monomer I and norbornene monomer J.The multipolymer (pJ) that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 160000, Mw/Mn is 3.3.

The hydrogenation of the ring opening copolymer thing (pJ) of＜norbornene monomer I and norbornene monomer J 〉

In the autoclave of capacity 0.2L, add pJ (1.66g), dimethylbenzene (150ml) and RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, with the reaction solution that obtains be cooled to 30 ℃, with the hydrogen release.Then, inject above-mentioned reaction solution in 2000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpJ)) 1.6g (productive rate 98%) of multipolymer (pJ).

The multipolymer (HpJ) that such operation is obtained confirmed by GPC, and the weight-average molecular weight of polystyrene conversion (Mw) is 131000, Mw/Mn is 3.6.In addition, use DSC to measure Tg, its as a result Tg be 137 ℃.Also to the multipolymer (HpJ) that obtains, the hydrogenation ratio that uses NMR mensuration alkene unsaturated link.The NMR figure of the multipolymer (HpJ) that expression obtains in Figure 10.From result shown in Figure 10 as can be known, in the hydride that obtains (HpJ), confirm that the hydrogenation ratio of alkene unsaturated link is 99.9%.In addition, in the hydride that obtains (HpJ), because do not change, so confirm that the aromatic rings of side chain is not hydrogenated in fact from the signal of aromatic rings.

(synthesis example 9)

＜norbornene monomer I and Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-copolymerization-3 of 3-dodecylene (norbornene monomer J) 〉

At first, preparation contains the norbornene monomer I (0.57g, 2.5mmol) that obtains and the anhydrous toluene solution (23ml) of the norbornene monomer J (1.20g, 7.5mmol) shown in the above-mentioned chemical formula (8) in synthesis example 5 under blanket of nitrogen, in above-mentioned anhydrous toluene solution (23ml), add the anhydrous toluene solution (2ml) contain 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stir 20 hours, obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, by the dry above-mentioned precipitation of vacuum drier, obtain ring opening copolymer thing (pK) 1.70g (productive rate 96%) of norbornene monomer I and norbornene monomer J.The multipolymer (pK) that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 123000, Mw/Mn is 2.6.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer I and norbornene monomer J (pK) 〉

In the autoclave of capacity 0.2L, add pK (1.66g), dimethylbenzene (150ml), RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, with the reaction solution that obtains be cooled to 30 ℃, with the hydrogen release.Then, inject this reaction solution in 2000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpK)) 1.6g (productive rate 98%) of pK.

The multipolymer (HpK) that such operation is obtained uses DSC to measure Tg, its as a result Tg be 147 ℃.In addition, multipolymer (HpK), use NMR are measured the hydrogenation ratio of alkene unsaturated link.The NMR figure that expression obtains in Figure 11.From result shown in Figure 11 as can be known, in the multipolymer that obtains (HpK), confirm that the hydrogenation ratio of alkene unsaturated link is 97.0%.In addition, in the multipolymer that obtains (HpK), because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.

(synthesis example 10)

＜norbornene monomer I and Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-copolymerization-4 of 3-dodecylene (norbornene monomer J) 〉

At first, preparation contains the norbornene monomer I (1.98g, 8.75mmol) that obtains and the anhydrous toluene solution (23ml) of the norbornene monomer J (0.20g, 1.25mmol) shown in the above-mentioned chemical formula (8) in synthesis example 5 under blanket of nitrogen, in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) contain 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stir 20 hours, obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, by the dry above-mentioned precipitation of vacuum drier, obtain ring opening copolymer thing (pL) 1.74g (productive rate 80%) of norbornene monomer I and norbornene monomer J.

The hydrogenation of the ring opening copolymer thing (pL) of＜norbornene monomer I and norbornene monomer J 〉

In the autoclave of capacity 0.2L, add pL (1.66g), dimethylbenzene (150ml), RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, with the reaction solution that obtains be cooled to 30 ℃, with the hydrogen release.Then, inject this reaction solution in 2000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpL)) 1.3g (productive rate 80%) of pL.

The multipolymer (HpL) that such operation is obtained uses DSC to measure Tg, its as a result Tg be 116 ℃.In addition, to the multipolymer (HpL) that obtains, the hydrogenation ratio that uses NMR mensuration alkene unsaturated link, confirm that above-mentioned hydrogenation ratio is 99.9%.In addition, in the multipolymer that obtains (HpL), because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.

(synthesis example 11)

＜norbornene monomer I and Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-copolymerization-5 of 3-dodecylene (norbornene monomer J) 〉

At first, preparation contains the norbornene monomer I (2.15g, 9.50mmol) that obtains and the anhydrous toluene solution (23ml) of the norbornene monomer J (0.08g, 0.5mmol) shown in the above-mentioned chemical formula (8) in synthesis example 5 under blanket of nitrogen, in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) contain 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stir 20 hours, obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, by the dry above-mentioned precipitation of vacuum drier, obtain ring opening copolymer thing (pM) 1.81g (productive rate 81%) of norbornene monomer I and norbornene monomer J.

The hydrogenation of the ring-opening polymerization polymer of＜norbornene monomer I and norbornene monomer J (pM) 〉

In the autoclave of capacity 0.2L, add pM (1.66g), dimethylbenzene (150ml), RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, with the reaction solution that obtains be cooled to 30 ℃, with the hydrogen release.Then, inject this reaction solution in 2000ml methyl alcohol, separate and reclaim precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpM)) 1.35g (productive rate 82%) of pM.

The multipolymer (HpM) that such operation is obtained uses DSC to measure Tg, its as a result Tg be 112 ℃.In addition, to the multipolymer (HpM) that obtains, the hydrogenation ratio that uses NMR mensuration alkene unsaturated link, confirm that above-mentioned hydrogenation ratio is 99.9%.In addition, in the multipolymer that obtains (HpM), because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.

(synthesis example 12)

＜norbornene monomer I and 8-methoxycarbonyl-8-methyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The copolymerization-1 of]-3-dodecylene (norbornene monomer K) 〉

At first, under blanket of nitrogen preparation contain the norbornene monomer I (1.13g, 5.0mmol) that in synthesis example 5, obtains and the norbornene monomer K shown in the following chemical formula (9) (1.16g, 5.0mmol, interior type/external form compare=79.2/20.8) anhydrous toluene solution (23ml).

In above-mentioned anhydrous toluene solution (23ml), add the anhydrous toluene solution (2ml) contain 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stir 20 hours, obtain polymer fluid.Then, the polymer fluid of the thickness that obtains with the 200ml dilution with toluene is put in the 3000ml methyl alcohol, filters the precipitation that obtains.Then, drying precipitated by vacuum drier, obtain ring opening copolymer thing (pN) 1.88g (productive rate 82%) of norbornene monomer I and norbornene monomer K.The multipolymer (pN) that obtains is confirmed by GPC the weight-average molecular weight of polystyrene conversion (Mw) is 147000, Mw/Mn is 4.5.

The hydrogenation of the ring opening copolymer thing (pN) of＜norbornene monomer I and norbornene monomer K 〉

In the autoclave of capacity 0.2L, add pN (1.68g), dimethylbenzene (150ml), RuHCl (CO) (PPh ₃) ₃(8.5mg, 0.5mass%), nitrogen replacement.Then, after heating 30 hours under the condition of 165 ℃ of Hydrogen Vapor Pressure 10MPa, temperature of reaction, carrying out hydrogenation, the reaction solution that cooling obtains, with the hydrogen release.Then, this reaction solution is injected in the 2000ml methyl alcohol, separate reclaims precipitation, the precipitation that drying obtains obtains hydride (multipolymer (the HpN)) 1.36g (productive rate 81%) of pN.

The multipolymer (HpN) that such operation is obtained confirmed by GPC, and the weight-average molecular weight of polystyrene conversion (Mw) is 129000, Mw/Mn is 4.1.In addition, to the multipolymer (HpN) that obtains, use DSC to measure Tg, its as a result Tg be 147 ℃.Also use NMR to measure the hydrogenation ratio of alkene unsaturated link, confirm that hydrogenation ratio is 99.9% the multipolymer (HpN) that obtains.In addition, in the multipolymer that obtains (HpN), because do not change, so confirm that aromatic rings is not hydrogenated in fact from the signal of aromatic rings.

(relatively synthesis example 1)

＜Fourth Ring [4.4.1 ^2,5.1 ^7,10.0]-polymerization of 3-dodecylene (norbornene monomer J) 〉

Under blanket of nitrogen, in the anhydrous toluene solution (23ml) of norbornene monomer J (1.60g, 10.0mmol), add the anhydrous toluene solution (2ml) that contains 1-hexene (75 μ l, 0.6mol%) and Grubbs I catalyzer (4.1mg, 0.05mol%), at room temperature stirred 20 hours.But, inhomogeneous, the polymer precipitation of reaction system, the polymkeric substance that obtains (pO) is insoluble in chloroform, THF etc.

(embodiment 9～14)

Use the multipolymer that in synthesis example 7～12, obtains { HpI that in synthesis example 7, obtains (embodiment 9), the HpJ (embodiment 10) that in synthesis example 8, obtains, the HpK (embodiment 11) that in synthesis example 9, obtains, the HpL (embodiment 12) that in synthesis example 10, obtains, the HpM (embodiment 13) that in synthesis example 11, obtains, the HpN (embodiment 14) that in synthesis example 12, obtains } respectively, make phase retardation film of the present invention (embodiment 9～14).

That is, preparing the chlorobenzene solution that contains each multipolymer with 5wt% concentration at first respectively, is membranaceous, air dry 24 hours by casting method with above-mentioned solution casting on glass plate, obtains the film precursor.Then, after the film precursor that obtains peeled off from glass plate respectively, use remains near the vacuum drier of the temperature (Tg-10 of each polymkeric substance ℃) of Tg of the polymkeric substance that becomes each membrane material, and being dried to residual solvent concentration becomes below the 1.0 quality %, obtains the film that is made of each multipolymer respectively.The transparency of operating the film that obtains like this is all very high.The thickness of the film that obtains in addition, is 30～150 μ m.

Then, the film that obtains is cut to thin oblong-shaped (size: 5.0 * 4.0cm) respectively, use biaxial stretch-formed device (production of bavin mountain science, SS-60 type), becoming under the temperature conditions of the polymer Tg of each membrane material+10 ℃, carry out the uniaxial tension of 200% (2.0 times) with the draw speed of 50mm/min, obtain phase retardation film of the present invention (embodiment 9～14).

(evaluation of the optical characteristics of the phase retardation film that in embodiment 9～14, obtains)

By postponing the birefringence that analyzer (production of prince's instrumentation society, trade name " KOBRA21DH ") is determined at the phase retardation film that obtains among the embodiment 9～14.In addition, refractive index utilizes the trade name " 2010 Prism Coupler " of Metricon society production to measure as the determinator of refractive index.In addition, the draw direction of the uniaxial tension of above-mentioned film is defined as X-axis, and will be defined as Y-axis and Z axle (Y-axis and Z axle be quadrature also), measure the refractive index (Nx) of X-axis, the refractive index (Ny) of Y-axis, the refractive index (Nz) of Z axle with the direction of X-axis quadrature.The result that expression obtains in table 2.

[table 2]

	Postpone (nm)	Nx	Ny	Nz	Thickness (μ m)	Ripple fear dispersion value D ^*1	(adding) ratio of monomer I
	Postpone (nm)	Nx	Ny	Nz	Thickness (μ m)	Ripple fear dispersion value D ^*1	(adding) ratio of monomer I	Embodiment 9 (HpI)	12.4	1.538	1.537	1.537	79	0.16	75
Embodiment 10 (HpJ)	197.9	1.536	1.534	1.534	93	0.94	50	Embodiment 9 (HpI)	12.4	1.538	1.537	1.537	79	0.16	75
Embodiment 10 (HpJ)	197.9	1.536	1.534	1.534	93	0.94	50	Embodiment 11 (HpK)	307.5	1.533	1.529	1.529	75	1.02	25
Embodiment 12 (HpL)	78.3	1.540	1.541	1.541	87	1.47	87.5	Embodiment 11 (HpK)	307.5	1.533	1.529	1.529	75	1.02	25
Embodiment 12 (HpL)	78.3	1.540	1.541	1.541	87	1.47	87.5	Embodiment 13 (HpM)	102.1	1.541	1.543	1.543	60	1.20	95
Embodiment 14 (HpN)	49.5	1.549	1.549	1.549	99	0.71	50	Embodiment 13 (HpM)	102.1	1.541	1.543	1.543	60	1.20	95

＊1 Δn@481nm/Δn@589nm

In addition, about the phase retardation film that obtains in embodiment 9～13, expression shows the ratio of the norbornene monomer I that contains and the chart of birefringent relation in Figure 12.In addition, about the phase retardation film that in embodiment 9～13, obtains, the ratio of the norbornene monomer I that the expression demonstration contains in Figure 13 and wavelength dispersion value { D=(Δ n: λ 481nm)/(Δ n: the chart of } relation λ 589nm).On the other hand, about the phase retardation film that in embodiment 9～13, obtains, the chart of the ratio of the norbornene monomer I that the expression demonstration contains in Figure 14 and the relation of Tg.In Figure 14, the ratio of norbornene monomer I and J (norbornene monomer I/ norbornene monomer J) is that 0/100 Tg (162 ℃) quotes Japanization association will 1998, No.2,81 pages.In addition, norbornene monomer I is that the interior type/external form of spatial configuration of the aromatic rings of side chain is 0/100 monomer than (isomer ratio).

From table 2 and result shown in Figure 12 as can be known, confirm that the phase retardation film that obtains is the film as phase retardation film performance good function in each embodiment.Also because the phase retardation film (embodiment 12) of HpL and the phase retardation film (embodiment 13) of HpM satisfy the relation shown in the following relational expression (1), so be confirmed to be film as so-called negative A phase retardation film performance function.

Ny＝Nz>Nx (1)

In addition, from result shown in Figure 13 as can be known, confirm each phase retardation film birefringent wavelength dispersion value D=(Δ n: λ 481nm)/(Δ n: λ 589nm) } according to the copolymerization ratio and difference,, confirm to become the contrary phase retardation film that disperses about the phase retardation film that in embodiment 9 and 10, obtains.

(evaluation of the adaptation of the phase retardation film that in embodiment 9～14, obtains)

Make the phase retardation film that in embodiment 9～14, obtains bonding with ultraviolet-curing adhesive (the synthetic production in East Asia, UVX-1620) on the surface of triacetyl cellulose substrate, method according to the JISK5400 record, when estimating their adaptation of phase retardation film, confirm that the adaptation of any one phase retardation film and tri acetyl cellulose membrane is all very high.

Utilizability on industry

As described above, can provide individual layer to have the high transparency and excellent wavelength dispersing characteristic according to the present invention, can give to the light of wide region specific phase difference, very high with the adaptation of other material, even and also can reach optical characteristics as special negative A in negative birefringence, and can make birefringent wavelength dispersing characteristic become the contrary phase difference film that disperses, and the liquid crystal indicator that uses this phase difference film.

Therefore, phase difference film of the present invention is useful especially as 1/2 λ plate of use in liquid crystal indicator etc., 1/4 λ plate, diaphragm, antireflection film etc.

Claims

1. phase retardation film is characterized in that:

It stretches the film that is formed by norborene class ring-opening polymerization polymer and obtains,

This norborene class ring-opening polymerization polymer contains the structural unit (A) shown in the following general formula (1), and in described structural unit (A), following wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles more than the %, the 100 moles scopes below the %

In the formula (1), n represents 0 or 1 integer,

X ¹Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ¹, R ², R ³And R ⁴Identical or different, expression is selected from any one atom or the base in hydrogen atom, halogen atom, alkyl and the polar group respectively, described alkyl is to have at least a kind of alkyl that is connected the carbon number 1～30 of basic replacement or non-replacement that is selected from oxygen atom, nitrogen-atoms, sulphur atom and the silicon atom

The spatial configuration of type or external form in wave-like line c represents.

2. phase retardation film as claimed in claim 1 is characterized in that:

In described structural unit (A), described wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles of scopes more than the %, less than 65 moles of %, and described phase retardation film is the contrary phase retardation film that disperses.

3. phase retardation film as claimed in claim 1 is characterized in that:

In described structural unit (A), described wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 65 moles more than the %, the 100 moles scopes below the %, and described phase retardation film is negative A phase retardation film.

4. phase retardation film as claimed in claim 3 is characterized in that:

When the draw direction with the uniaxial tension of described film is defined as X-axis and will be defined as Y-axis and Z axle with the direction of X-axis quadrature, the refractive index (Ny) of the refractive index of X-axis (Nx), Y-axis and the refractive index (Nz) of Z axle satisfy the relation shown in the following relational expression (1)

Ny＝Nz>Nx (1)。

5. phase retardation film as claimed in claim 1 is characterized in that:

X in the described general formula (1) ¹Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, be 90 moles more than the % with respect to the entire infrastructure unit in the described norborene class ring-opening polymerization polymer.

6. phase retardation film as claimed in claim 1 is characterized in that:

Described norborene class ring-opening polymerization polymer is a norborene class ring opening copolymer thing, this norborene class ring opening copolymer thing contains the structural unit (B) shown in structural unit (A ') shown in the following general formula (2) and the following general formula (3), and in described structural unit (A '), the spatial configuration of the replacement in the described general formula (2) or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio in 90 moles of scopes more than the %

In the formula (2), n, X ¹, R ¹, R ², R ³, R ⁴With n, the X in wave-like line c and the described general formula (1) ¹, R ¹, R ², R ³, R ⁴With the same meaning of wave-like line c,

In the formula (3), n represents 0 or 1 integer,

X ²Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ⁵, R ⁶, R ⁷, R ⁸Identical or different, respectively expression be selected from alkyl, the carbon number 1～20 of hydrogen atom, halogen atom, cyano group, carbon number 1～20 thiazolinyl, carbon number 1～20 alkyl-carbonyl and have any one atom or base in the ester group of alkyl of carbon number 1～20

R ⁵And R ⁶, or, R ⁷And R ⁸Can form the alkylidene of carbon number 1～20 together.

7. phase retardation film as claimed in claim 6 is characterized in that:

Described structural unit (A '-1) contain ratio, in 40 moles of scopes more than the %, less than 80 moles of %, and described phase retardation film is the contrary phase retardation film that disperses with respect to the entire infrastructure unit in the described norborene class ring opening copolymer thing.

8. phase retardation film as claimed in claim 6 is characterized in that:

Described structural unit (A '-1) contain ratio, in 80 moles more than the %, the 99 moles scopes below the %, and described phase retardation film is negative A phase retardation film with respect to the entire infrastructure unit in the described norborene class ring opening copolymer thing.

9. phase retardation film as claimed in claim 8 is characterized in that:

Satisfy the relation shown in the described relational expression (1).

10. phase retardation film as claimed in claim 6 is characterized in that:

X in the described general formula (2) ¹Be formula-CH ₂CH ₂-shown in the structural unit of base and the X in the described general formula (3) ²Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, be 90 moles more than the % with respect to the entire infrastructure unit in the described norborene class ring-opening polymerization polymer.

11. a liquid crystal indicator is characterized in that:

Has the described phase retardation film of claim 1.