CN101155897A - Polymerizable liquid crystal composition, optical anisotropic material, optical element, and optical head device - Google Patents
Polymerizable liquid crystal composition, optical anisotropic material, optical element, and optical head device Download PDFInfo
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- CN101155897A CN101155897A CNA2006800117216A CN200680011721A CN101155897A CN 101155897 A CN101155897 A CN 101155897A CN A2006800117216 A CNA2006800117216 A CN A2006800117216A CN 200680011721 A CN200680011721 A CN 200680011721A CN 101155897 A CN101155897 A CN 101155897A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims description 76
- 239000000203 mixture Substances 0.000 title abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 226
- -1 naphthalenediyl group Chemical group 0.000 claims abstract description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 18
- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
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- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
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- 125000005647 linker group Chemical group 0.000 abstract 2
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 abstract 1
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- 239000002585 base Substances 0.000 description 55
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- 239000006185 dispersion Substances 0.000 description 19
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- 238000000034 method Methods 0.000 description 18
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention provides a phase plate suitable for use in a broadband, an optical element such as a polarizing diffractive element having an excellent diffraction efficiency, a polymerizable liquid crystal composition for use in them, and an optical head device using them. A polymerizable liquid crystal composition comprises a polymerizable compound having a mesogen structure comprising the following six-membered ring group (B) attached to at least one bonding hand in the following condensed benzene ring group (A) either directly or through a linking group of -OCO- or -COO-, and a monovalent end group attached to each of both ends in the mesogen structure, at least one of the end groups being a monovalent organic group having a polymerizable site. Condensed benzene ring group (A): a naphthalenediyl group having a bonding hand at the 1-position, 4-position, or 5-position, or an anthracenediyl group having a bonding hand at the 1-position or 9-position and the 4-position, 5-position, or 10-position. Six-membered ring group (B): a divalent group to which a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or two or more groups selected from these groups are attached either directly or through a linking group.
Description
Technical field
The present invention relates to for the useful polymerizable compound of the modulation of the optical anisotropic material of the anisotropic wavelength dispersion of may command specific refractory power, contain the polymerizable liquid crystal compound of this polymerizable compound and used the optical element and the optical-head apparatus of said composition.
Background technology
Liquid crystal molecule with polymerizability functional group has concurrently as the character of polymerizable monomer with as the character of liquid crystal.Therefore, if so that the behavior aggregate of its orientation then obtains the polymkeric substance that orientation is fixed, that is, and optical anisotropic material.The optical anisotropic material that obtains like this has based on the anisotropic optical anisotropy of specific refractory power from mesomorphic unit (mesogenic unit) skeleton, utilizes this character to can be applicable to optical elements such as phase retardation plate, diffraction element.
The known phase retardation plate of high molecule liquid crystal that used is compared with the phase retardation plate that has used low molecular weight liquid crystal, and the temperature dependency of phase differential (or lagged value) is little.
As this phase retardation plate, the phase differential of for example having put down in writing phase differential with birefringent light in the patent documentation 1 and be the quarter wave plate of 1/4 wavelength and birefringent light is the phase retardation plate that state that 1/2 wave plate of 1/2 wavelength intersects with their optical axis fits into feature.Also put down in writing stacked quarter wave plate and 1/2 wave plate that polymeric membrane (particularly polycarbonate) is carried out stretch processing and get, made the technical scheme of this phase retardation plate.But there is necessary stacked polylith wave plate in the phase retardation plate that patent documentation 1 is put down in writing and needs the problem of complicated manufacturing process.
In addition, patent documentation 2 has been put down in writing the phase retardation film with following feature, promptly, this phase retardation film possesses the compound of the mesomorphic unit base that contains more than 2 kinds and the liquid crystal layer of rod shaped liquid crystal compound, the rod shaped liquid crystal compound is even orientation, and at least a kind of mesomorphic unit base of compound with mesomorphic unit base is with respect to the optical axis direction of the rod shaped liquid crystal compound directions orientation with 45～90 degree in face.Also put down in writing the phase retardation plate that to make the wavelength dispersion of utilizing phase differential by this.But, owing to need contain these the two kinds of different materials of compound and rod shaped liquid crystal compound of the mesomorphic unit base more than 2 kinds, therefore exist and various groups of satisfying desired characteristic must be discussed be incorporated in selection in this combination, obtain the problem that the degree of freedom of suitable design aspects such as material is restricted.
In addition, put down in writing 4 membered ring compounds of following general formula (I) expression in the patent documentation 3, also put down in writing by this phase retardation plate of wavelength dispersion that can the production control phase differential.
General formula (I)
(in the formula, X
1And X
2Represent Sauerstoffatom, sulphur atom etc., Y respectively independently
1And Y
2Represent singly-bound, Sauerstoffatom etc., B respectively independently
1And B
2Expression can have the aliphatic group etc. of substituent carbon number 1～20 independently respectively, and two phenyl ring that are directly connected in the tetramethylene ring can have substituting group, A respectively on ring
1And A
2The group of representing following general formula (II) expression respectively independently.)
General formula (II)
(in the formula, Ar
1, Ar
2And Ar
3Represent the cyclic group of carbon number 5～14 etc. respectively independently, L
1And L
2Represent the connection base of singly-bound or divalence respectively independently, p represents 0～2 arbitrary integer, and p is 2 o'clock, 2 Ar
2And L
2Can be identical or different respectively.)
On the other hand, show in the patent documentation 4 of the tolane liquid crystal that uses in the liquid crystal cell of usefulness as being conceived to high meticulous polymer-dispersed liquid crystal, as polymerizable liquid crystal compound, put down in writing have-C ≡ C-is as the liquid crystalline cpd that connects base.As one of its a plurality of examples, in [0083] paragraph, to have put down in writing as followsly at naphthalene-1,4-two bases and 1 are provided with between the 4-phenylene-C ≡ C-connects the polymerizable liquid crystal compound that the following general formula (III) of base is represented.
General formula (III)
(in the formula, R
1Expression hydrogen atom, alkyl, phenyl or halogen.)
Patent documentation 1: Japanese patent laid-open 10-68816 communique
Patent documentation 2: the Japanese Patent spy opens the 2002-267838 communique
Patent documentation 3: the Japanese Patent spy opens the 2003-160540 communique
Patent documentation 4: Japanese patent laid-open 07-082183 communique
The announcement of invention
But even the known phase retardation plate that has used 4 membered ring compounds of record in the above-mentioned patent documentation 3, the wavelength dispersion characteristic also can't be fully improved sometimes.In addition, chemically unsettled tetramethylene ring can because phase retardation plate when making light and heat or under working conditions, decompose, have the problem of wavelength dispersion deterioration in characteristics.
In addition, the purpose of the compound of patent documentation 4 records is to increase the specific refractory power anisotropy by prolonging conjugate length.The anisotropic wavelength dependency of known specific refractory power in this case becomes big.Therefore, used the wave plate of this compound to have the problem of wavelength dispersion deterioration in characteristics.
Aspect the control wavelength dispersion, less for the research that reduces the anisotropic wavelength dependency of specific refractory power, particularly the liquid crystal material that increases along with the increase of using wavelength of specific refractory power anisotropy well needs because of the application in broad frequency range very much, but but finds the degree of freedom material of use greatly and stably at present.
The present invention is the invention of finishing in view of above-mentioned variety of issue, the optical-head apparatus that its problem provides optical elements such as the good polarized light diffraction element of the phase retardation plate, the diffraction efficiency that are applicable to broad frequency range and is used to the polymerizable liquid crystal compound of these optical elements and used these optical elements.
The inventor conscientiously studies the back discovery for solving above-mentioned problem, the optical anisotropic material that the polymerizable liquid crystal compound of the polymerizable compound that comprises the mesomorphic unit with regulation is polymerized can be controlled the anisotropic wavelength dispersion of specific refractory power at intramolecularly, thereby has finished the present invention.
That is, the invention provides following (I)～(XIII).
(I) polymerizable liquid crystal compound, wherein, comprise and have mesomorphic unit and be polymerizable compound (following also note is done " polymerizable compound (3) ") at least one side of two terminal bonded 1 valency end groups of this mesomorphic unit, this end group respectively with the 1 valency organic group at polymerizability position, described mesomorphic unit by at least one side's of following fused benzene rings base (A) associative key directly or be situated between with as connection basic-OCO-or-COO-obtains in conjunction with following 6 yuan of cyclic groups (B); Fused benzene rings base (A): at 1 and 4 or 5 naphthalene with associative key, two bases or at 1 or 9 and 4,5 or 10 anthracene two bases with associative key, 6 yuan of cyclic groups (B): 1,4-phenylene, anti--1, the 4-cyclohexylidene or by the group more than 2 that is selected from these groups directly or be situated between with connect base in conjunction with and the divalent group.
(II), wherein, contain following formula (1) as above-mentioned (I) described polymerizable liquid crystal compound
CH
2＝CR
1-COO-J
1-(E
1-J
2)
n-W
1-J
3-M-R
2……(1)
The polymerizable compound of expression, the R in the formula
1, R
2, n, J
1, J
2, J
3, E
1, W
1And the implication of M is as described below:
R
1: hydrogen atom or methyl, R
2: the alkyl of carbon number 2～8, n:0 or 1, J
1: singly-bound ,-(CH
2)
a-or-(CH
2)
bO-, a wherein and b are respectively 2～8 integer independently, J
2, J
3: respectively be independently singly-bound ,-OCO-or-COO-, E
1: 1,4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
1: naphthalene-1,4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,10-two bases, hydrogen atom in these groups can be replaced M: be selected from following formula (a)～(f) by chlorine atom, fluorine atom, methyl or cyano group
Arbitrary group of the group of expression.
(III), wherein, contain M for being selected from following formula (a)～(e) as above-mentioned (II) described polymerizable liquid crystal compound
The polymerizable compound of arbitrary group of the group of expression.
(IV), wherein, contain M for anti--1,4-cyclohexylidene or anti-, the polymerizable compound of anti--4,4 '-two cyclohexylidenes as above-mentioned (III) described polymerizable liquid crystal compound.
(V), wherein, contain following formula (2) as above-mentioned (I) described polymerizable liquid crystal compound
CH
2＝CR
3-COO-J
4-E
2-COO-W
2-OCO-E
3-J
5-OCO-CR
3＝CH
2……(2)
The polymerizable compound of expression, the R in the formula
3, J
4, J
5, E
2, E
3And W
2Implication as described below:
R
3: hydrogen atom or methyl, J
4:-(CH
2)
tO-or-(CH
2)
uO-CO-, wherein, t and u are respectively 2～6 integer independently, J
5:-O (CH
2)
c-or-COO-(CH
2)
d-, wherein, c and d are respectively 2～6 integer independently, E
2, E
3: be respectively 1 independently, 4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
2: naphthalene-1,4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,10-two bases, the hydrogen atom in these groups can be replaced by chlorine atom, fluorine atom, methyl or cyano group.
(VI) polymerizable liquid crystal compound, wherein, in above-mentioned (I)～(V) content of each described polymerizable compound with respect to polymerizable liquid crystal compound more than 10 quality %.
(VII) optical anisotropic material wherein, makes each described polymerizable liquid crystal compound polymerization in above-mentioned (I)～(V) and gets.
(VIII) as above-mentioned (VII) described optical anisotropic material, wherein, described material is the optics uniaxiality, as ordinary refraction index n
oWith unusual optical index n
eThe value of specific refractory power anisotropy Δ n of difference increase along with the increase of used light wavelength.
(IX) optical element wherein, adopts above-mentioned (VII) or (VIII) described optical anisotropic material formation, controls used polarisation of light light state and/or phase state.
(X) phase retardation plate wherein, adopts above-mentioned (VII) or (VIII) described optical anisotropic material formation.
(XI) polarized light diffraction element, it is the polarized light diffraction element that possesses the diffraction grating zone of diffraction incident light, wherein, aforementioned diffraction grating zone possesses the 1st member that is formed by the 1st material and the 2nd member that is formed by the 2nd material, aforementioned the 1st member is different at least a polarized light refractive index with aforementioned the 2nd member, aforementioned the 1st member and aforementioned the 2nd member be with the state configuration that is connected alternate with each other, and aforementioned the 1st material is above-mentioned (VII) or (VIII) described optical anisotropic material.
(XII) optical-head apparatus, it is by semiconductor laser, object lens, photodetector, is disposed at the optical-head apparatus that phase retardation plate between aforementioned object lens and the aforementioned lights detector and/or polarized light diffraction element constitute, wherein, aforementioned phase retardation plate is that above-mentioned (X) described phase retardation plate and/or aforementioned polarized light diffraction element are above-mentioned (XI) described polarized light diffraction element.
(XIII) following formula (1) or (2)
CH
2＝CR
1-COO-J
1-(E
1-J
2)
n-W
1-J
3-M-R
2……(1)
CH
2＝CR
3-COO-J
4-E
2-COO-W
2-OCO-E
3-J
5-OCO-CR
3＝CH
2……(2)
The polymerizable compound of expression, the R in the formula
1, R
2, R
3, n, J
1, J
2, J
3, J
4, J
5, E
1, E
2, E
3, W
1, W
2And the implication of M is as described below:
R
1, R
3: be hydrogen atom or methyl independently respectively, R
2: the alkyl of carbon number 2～8, n:0 or 1, J
1: singly-bound ,-(CH
2)
a-or-(CH
2)
bO-, a wherein and b are respectively 2～8 integer independently, J
2, J
3: respectively be independently singly-bound ,-OCO-or-COO-, J
4:-(CH
2)
tO-or-(CH
2)
uO-CO-, wherein, t and u are respectively 2～6 integer independently, J
5:-O (CH
2)
c-or-COO-(CH
2)
d-, wherein, c and d are respectively 2～6 integer independently, E
1, E
2, E
3: be respectively 1 independently, 4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
1, W
2: be naphthalene-1 independently respectively, 4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,10-two bases, hydrogen atom in these groups can be replaced M: be selected from following formula (a)～(f) by chlorine atom, fluorine atom, methyl or cyano group
Arbitrary group of the group of expression.
If employing the present invention then can obtain for the useful polymerizable compound of the adjustment of the anisotropic wavelength dispersion of specific refractory power, comprise the polymerizable liquid crystal compound of this polymerizable compound.By using this polymerizable liquid crystal compound, can obtain the good polarized light diffraction element of the phase retardation plate that is particularly suitable in broad frequency range, using, the efficient of deriving of the wavelength dependency reduction of phase differential in certain wavelength region.
The simple declaration of accompanying drawing
The figure of the anisotropic wavelength dependency of specific refractory power of the phase retardation plate A that Fig. 1 obtains among the embodiment 7 for expression.
The figure of the anisotropic wavelength dependency of specific refractory power of the phase retardation plate B that Fig. 2 obtains among the embodiment 8 for expression.
Fig. 3 has used the concise and to the point side elevational view of an example of the optical-head apparatus of phase retardation plate of the present invention and polarized light diffraction element for expression.
Fig. 4 is the infrared absorption spectrum of compound (1A).
Fig. 5 is the infrared absorption spectrum of compound (1B).
Fig. 6 is the infrared absorption spectrum of compound (1C).
Fig. 7 is the infrared absorption spectrum of compound (2B).
Fig. 8 is the infrared absorption spectrum of compound (1U).
Fig. 9 is the infrared absorption spectrum of compound (1V).
Figure 10 is the infrared absorption spectrum of compound (1D).
Figure 11 is the infrared absorption spectrum of compound (1W).
The figure of the anisotropic wavelength dependency of specific refractory power of the phase retardation plate C that Figure 12 obtains among the embodiment 11 for expression.
The explanation of symbol
301,302: semiconductor laser, 304,305: photodetector, 308: close the ripple prism, 310: collimating lens, 311: polarized light diffraction element, 312: wideband phase retardation plate, 313: object lens, 314: actuator, 315: CD.
The best mode that carries out an invention
Polymerizable liquid crystal compound of the present invention is to comprise to have mesomorphic unit and be the polymerizable liquid crystal compound of polymerizable compound with the 1 valency organic group at polymerizability position at least one side of two terminal bonded 1 valency end groups of this mesomorphic unit, this end group respectively, described mesomorphic unit by at least one side's of following fused benzene rings base (A) associative key directly or be situated between with-OCO-basic as connecting or-COO-obtains in conjunction with following 6 yuan of cyclic groups (B).
Fused benzene rings base (A): at 1 and 4 or 5 naphthalene with associative key, two bases or at 1 or 9 and 4,5 or 10 anthracene two bases with associative key.
6 yuan of cyclic groups (B): 1,4-phenylene, anti--1, the 4-cyclohexylidene or by the group more than 2 that is selected from these groups directly or be situated between with connect base in conjunction with and the divalent group.
Above-mentioned fused benzene rings base (A) is meant the phenyl ring linearity condensed structure that has more than 2, and what 2 associative keys all were present in relative phenyl ring condenses on the vertical direction of direction and in the opposite direction divalent group respectively.Phenyl ring condensed quantity is 2 or 3, and good especially is 2.That is, above-mentioned fused benzene rings base (A) is basic or at 1 or 9 and 4,5 or 10 anthracene two bases with associative key, good especially is these naphthalene two bases for the naphthalene two that has an associative key at 1 and 4 or 5.
Above-mentioned 6 yuan of cyclic groups (B) are meant 1,4-phenylene, anti--1, the 4-cyclohexylidene or by the group more than 2 that is selected from these groups directly or be situated between with connect base (C) in conjunction with and the divalent group.Connect base (C) and be-OCO-or-COO-.
As 6 yuan of cyclic groups (B), for example better be 1,4-phenylene, anti--1,4-cyclohexylidene, following radicals (B1)～(B4), be more preferably instead-1,4-cyclohexylidene, following radicals (B1)～(B4) are owing to can give full play to the optically anisotropic effect of fused benzene rings base (A), good especially is anti--1,4-cyclohexylidene, following radicals (B1).
Above-mentioned polymerizable compound (3) have at least one side's of fused benzene rings base (A) associative key directly or be situated between with connect base (C) in conjunction with 6 yuan of cyclic groups (B) mesomorphic unit.
Connect base (C) and be-OCO-or-COO-.
As mesomorphic unit, for example better be structure shown below.
Two ends of above-mentioned mesomorphic unit are combined with the end group of 1 valency respectively.
As end group, preferably exemplified by alkyl groups, alkoxyl group, polymerizability functional group, have the 1 valency organic group at polymerizability position etc., good especially be alkyl, polymerizability functional group, have 1 a valency organic group at polymerizability position.In addition, at least one of end group is polymerizability functional group or 1 valency organic group with polymerizability position.
End group is under the situation of alkyl, better is the straight chained alkyl of carbon number 2～8, and good especially is the straight chained alkyl of carbon number 2～6.
In addition, end group is under the situation of alkoxyl group, better is the straight chain alkoxyl group of carbon number 2～8, and good especially is the straight chain alkoxyl group of carbon number 2～6.
In addition, end group is under the situation of polymerizability functional group, better is acryl, methacryloyl, and good especially is acryl.End group is to have under the situation of 1 valency organic group at polymerizability position, better is to have CH
2=CH-COO-part or CH
2=C (CH
3The organic group of)-COO-part, good especially is to have CH
2The organic group of=CH-COO-part.
As 1 valency organic group, for example better be group shown below with polymerizability position.
CH
2＝CH-COO-(CH
2)
2-O-、
CH
2＝CH-COO-(CH
2)
3-O-、
CH
2＝CH-COO-(CH
2)
4-O-、
CH
2＝CH-COO-(CH
2)
5-O-、
CH
2＝CH-COO-(CH
2)
4-OCO-。
In addition, the quantity that is incorporated into 6 yuan of cyclic groups (B) of fused benzene rings base (A) is under 1 the situation, better is the 1 valency organic group that is not combined with polymerizability functional group in conjunction with the associative key of 6 yuan of cyclic groups (B) or has the polymerizability position.
Among the present invention,, adopt this polymerizable compound (3) and the wavelength dispersion characteristic of the optical anisotropic material that obtains is good by using such polymerizable compound (3).
Another polymerizable liquid crystal compound of the present invention is to make according to application target in broad frequency range and the adjustment of the anisotropic wavelength dispersion of refractive index is easy to, and contains the polymerizable liquid crystal compound of the polymerizable compound (2) of the polymerizable compound (1) of following formula (1) expression more than 2 kinds and/or following formula (2) expression.
CH
2＝CR
1-COO-J
1-(E
1-J
2)
n-W
1-J
3-M-R
2……(1)
CH
2＝CR
3-COO-J
4-E
2-COO-W
2-OCO-E
3-J
5-OCO-CR
3＝CH
2……(2)
Among the present invention, polymerizable compound (1) and polymerizable compound (2) can be liquid crystal compounds or non-liquid crystal compounds, use these polymerizable compounds and the polymerizable liquid crystal compound that obtains shows nematic liquid crystal gets final product.But the high angle of degree of freedom when the polymerizable liquid crystal compound that obtains shows the modulation of liquid crystal liquid crystal property, composition easily better is a liquid crystal compounds.
In the above-mentioned formula (1), R
1It better is hydrogen atom.If R
1Be hydrogen atom, then have and carry out polyreaction described later and the fast advantage of polymerization velocity when obtaining optical anisotropic material.
R
2The structure of alkyl of carbon number 2～8 can be linear chain structure or branched structure, better be linear chain structure.In order to make polymerizable compound (1) show nematic phase, R well
2Carbon number better be 2～6.
The wavelength dispersion characteristic of polyreaction when making optical anisotropic material is good owing to carrying out, J
1It better is singly-bound.J
1For-(CH
2)
a-or-(CH
2)
bUnder the situation of O-, a and b are respectively 2～8 integer independently, better are 2～5 integers, and good especially is 2～4 integer.J
2And J
3Better be respectively-OCO-.Pass through J
2And J
3Be respectively-OCO-, the crystallization-nematic Phase point of polymerizable compound (1) can be not too high, has to handle to be easy to advantage.
E
1Be 1,4-phenylene or anti--1,4-cyclohexylidene.These groups can be not have the group that replaces, and also can be the groups that the hydrogen atom in this group is replaced by chlorine atom, fluorine atom, methyl or cyano group.From the good angle of liquid crystal liquid crystal property of polymerizable compound (1), E
1Better be the group that do not have to replace, from following viewpoint, good especially is not have replace anti--1,4-cyclohexylidene.That is W,
1Itself be exactly optically anisotropic macoradical, but because E
1Existence, W
1Optical anisotropy may diminish.Therefore, in order to effectively utilize W
1Optical anisotropy, E
1Optical anisotropy must be little, so think anti--1, the 4-cyclohexylidene than optical anisotropy high 1, the 4-phenylene is good.
W
1Better be naphthalene-1,4-two bases or naphthalene-1,5-two bases.These groups can be not have the group that replaces, and also can be the groups that the hydrogen atom in this group is replaced by chlorine atom, fluorine atom, methyl or cyano group.From the angle of the wavelength dispersion characteristic that improves optical anisotropic material, W
1It better is following radicals (60a)～(60c) (X in the formula represents chlorine atom, fluorine atom or cyano group).The effect that improves the wavelength dispersion characteristic of optical anisotropic material is followed successively by cyano group, chlorine atom, fluorine atom from big to small, considers that simultaneously suitable use of crystallization-nematic Phase point of polymerizable compound (1) gets final product.
M is the arbitrary group that is selected from the group of following formula (a)～(f) expression, owing to can effectively utilize W
1Optically anisotropic effect, better be following formula (a) or (b) expression group.
As polymerizable compound (1), for example better be following compound, good especially is following compound (1A)～(1C), (1D), (1L), (1N)～(1 Q), (1U), (1V), (1W).
In the above-mentioned formula (2), as R
3, according to R
1Same reason better is a hydrogen atom.
J
4For-(CH
2)
tO-or-(CH
2)
uO-CO-.T and u are respectively 2～6 integer independently.
J
5For-O (CH
2)
c-or-COO-(CH
2)
d-.C and d are respectively 2～6 integer independently.
E
2And E
3Be respectively 1 independently, 4-phenylene or anti--1,4-cyclohexylidene.Hydrogen atom in these groups can be replaced by chlorine atom, fluorine atom, methyl or cyano group.As E
2And E
3, owing to can effectively utilize W
2Optically anisotropic effect, better be respectively do not have to replace anti--1, the 4-cyclohexylidene.
W
2For with above-mentioned W
1Same group, preferred form is also identical.
As polymerizable compound (2), owing to can effectively utilize W
2Optically anisotropic effect, better be following compound (2A) and (2B).
Among the present invention, comprise the polymerizable compound (1) more than 2 kinds and/or the polymerizable liquid crystal compound of polymerizable compound (2) by employing, according to the application target in broad frequency range and the adjustment of the anisotropic wavelength dispersion of refractive index is easy, be ideal.
Especially, the present invention better is the polymerizable liquid crystal compound that comprises the polymerizable compound (1) more than 2 kinds, and good especially is the polymerizable liquid crystal compound that comprises the polymerizable compound (1) of 3 kinds or 4 kinds.Specifically, better be the polymerizable liquid crystal compound that comprises above-claimed cpd (1A)～(1C), comprise above-claimed cpd (1A)～(1C) and polymerizable liquid crystal compound (1U), comprise above-claimed cpd (1D) and polymerizable liquid crystal compound (1W).
In the polymerizable liquid crystal compound of the present invention, the content of above-mentioned polymerizable compound better is more than 10 quality % with respect to polymerizable liquid crystal compound, is more preferably 20～100 quality %, and good especially is 50～100 quality %.Content that it is generally acknowledged polymerizable compound is big more, and then the anisotropic wavelength dispersion characteristic of specific refractory power is good more.
In addition, polymerizable liquid crystal compound of the present invention can comprise other compound (hereinafter referred to as " other compound ") except that above-mentioned polymerizable compound.As other compound, can exemplify polymerizable liquid crystal compound and the non-liquid crystal compounds of polymerizability except that above-mentioned polymerizable compound.
As the polymerizable liquid crystal compound,, be not particularly limited so long as the compound that has mesomorphic unit and polymerizability functional group and show liquid crystal liquid crystal property gets final product.For example, can the exemplified by acrylic ester compound, methyl acrylic ester compound, siloxane compound, epoxy compounds etc., owing to have good photopolymerization characteristic, better be acrylic ester compound and methyl acrylic ester compound.
In addition, other polymerizable liquid crystal compound has under the situation of a plurality of polymerizability functional group, and the kind of polymerizability functional group can be identical or different.Particularly use to have under the situation of 2 polymerizability functional groups, can obtain good thermotolerance and strength characteristics, so be ideal.
As other polymerizable liquid crystal compound, specifically can exemplify following compound (30), (40), (50) etc. (with reference to Japanese patent laid-open 10-265531 communique etc.).
Compound (30)
(in the formula, A
4Be fluorine atom, chlorine atom, hydrogen atom or methyl, m is 0～8 integer, m be 0 or 1 o'clock r be 0, the r when m is 2～8 integer is 1, X
3For singly-bound ,-COO-,-OCO-or-CH
2CH
2-, s is 0 or 1, and k is 0 or 1, and k is 0 o'clock X
4Be singly-bound, k is 1 o'clock X
4For with X
3Identical structure.)
Compound (40)
(in the formula, A
5Be fluorine atom, chlorine atom, hydrogen atom or methyl, v is 0～8 integer, v be 0 or 1 o'clock w be 0, the w when v is 2～8 integer is 1, X
5For singly-bound ,-COO-,-OCO-or-CH
2CH
2-, Y
1Be 1,4-phenylene or anti--1,4-cyclohexylidene, Z
1Alkoxyl group, fluorine atom, chlorine atom or cyano group for carbon number 1～8.)
In addition, as other polymerizable liquid crystal compound, the compound that can also use following general formula to represent.
Compound (50)
(in the formula, X
6Be 1,4-phenylene or anti--1,4-cyclohexylidene, Y
2Alkyl for carbon number 1～8.)
As compound (30), better be following compound.
As compound (40), better be following compound.
As compound (50), better be following compound (wherein, 1, the 4-phenylene is expressed as Ph, and is anti--1, the 4-cyclohexylidene is expressed as Cy).
■ H
2C＝CH-COO-Ph-OCO-Cy-n-C
3H
7
■ H
2C＝CH-COO-Ph-OCO-Cy-n-C
4H
9
■ H
2C＝CH-COO-Ph-OCO-Cy-n-C
5H
11
■ H
2C＝CH-COO-Ph-OCO-Ph-n-C
3H
7
■ H
2C＝CH-COO-Ph-OCO-Ph-n-C
4H
9
■ H
2C＝CH-COO-Ph-OCO-Ph-n-
C5H
11
As the non-liquid crystal compounds of polymerizability, can exemplified by acrylic ester class, methyl acrylic ester, vinyl ethers etc.Their usage quantity better is below 5 quality % with respect to polymerizable liquid crystal compound, and good especially is below the 1 quality %.
For polyreaction described later is successfully carried out, polymerizable liquid crystal compound of the present invention better is to contain polymerization starter.
As polymerization starter, for example can exemplify thermal polymerizations such as superoxide, azo-compound, Photoepolymerizationinitiater initiaters such as acetophenones, Benzophenones, bitter almond oil camphor class, benzyl class, Michler's keton, benzoin alkylether class, benzyl dimethyl ketal class, thioxanthene ketone etc., they may be used alone, two or more kinds can also be used.The amount of polymerization starter better is 0.1～10 quality % with respect to polymerizable liquid crystal compound, and good especially is 0.3～2 quality %.
In addition, polymerizable liquid crystal compound of the present invention can comprise stablizer, UV light absorber etc.As stablizer, for example can exemplify Resorcinol, Resorcinol monoalkyl ethers, tert-butyl catechol class etc., they may be used alone, two or more kinds can also be used.The content of stablizer, UV light absorber etc. better is below 1 quality % with respect to polymerizable liquid crystal compound, and good especially is below 0.5 quality %.
Optical anisotropic material of the present invention is the optical anisotropic material that above-mentioned polymerizable liquid crystal compound polymerization of the present invention is got.Polyreaction better is that above-mentioned polymerizable liquid crystal compound is injected in the box of orientation process, carries out under the state of the liquid crystal aligning in said composition.As polyreaction, can exemplify photopolymerization reaction, heat polymerization etc., better be photopolymerization reaction.
As the used light of photopolymerization reaction, can exemplify ultraviolet ray, visible light etc., better be ultraviolet ray.In addition, carry out under the situation of photopolymerization reaction, if use above-mentioned then polymerization efficiently of Photoepolymerizationinitiater initiater.
Optical anisotropic material of the present invention better is to be the optics uniaxiality, as ordinary refraction index n
oWith unusual optical index n
eThe material that increases along with the increase of used light wavelength of the value of specific refractory power anisotropy Δ n of difference.Usually, constant if the specific refractory power anisotropy is not subjected to the influence of wavelength, the phase differential that produces based on the specific refractory power anisotropy reduces with the increase of light wavelength.
Therefore, if phase retardation plate and diffraction element under certain wavelengths by optimization, then along with the increase of used light wavelength, can can't play the effect of phase retardation plate, perhaps the decrease in efficiency of diffraction element.On the other hand, if the material that the specific refractory power anisotropy increases along with the increase of used light wavelength, can suppress to follow the reduction of phase differential of the increase of light wavelength, so can make it fully play the effect of wide band phase retardation plate and diffraction element.That is, can be well as the polarisation of light light state that uses in certain wavelength region may inner control and/or the optical element of phase state.
Optical element of the present invention is to adopt optical anisotropic material of the present invention to form, and controls the optical element of used polarisation of light light state and/or phase state.
As such optical element, can exemplify phase retardation plate, polarized light diffraction element etc.As phase retardation plate, certainly control the phase place of the laser of single wavelength, also can be used as the wideband phase retardation plate of the phase place of the laser of controlling the multi-wavelength in certain wavelength region may well.As the polarized light diffraction element, can be implemented in the laser-transmitting of the diffraction element that all has high-diffraction efficiency under the arbitrary wavelength among the used multi-wavelength and specific wavelength and the diffraction element of the laser of diffraction specific wavelength only.As the object lesson of polarized light diffraction element, can exemplify polarized light beam splitter and polarizing prism.Can make they have light convergence, disperse function, also can make them have wavelength selectivity.
By embodiment 5 described later and Fig. 1 (figure of the anisotropic wavelength dependency of specific refractory power of the phase retardation plate that obtains among the expression embodiment 5) also as can be known, optical anisotropic material of the present invention in the specific refractory power anisotropy along with the increase of light wavelength aspect the increase, above-mentioned wavelength dispersion characteristic is good, use the wavelength dispersion that phase retardation plate of the present invention that this optical anisotropic material forms can the control phase difference, therefore very useful.
As phase retardation plate of the present invention, can exemplify quarter wave plate, 1/2 wave plate etc.The direction of the rectilinearly polarized light of the direction that quarter wave plate makes after optical recording medium reflection once more the rectilinearly polarized light behind the transmission quarter wave plate before with respect to the incident quarter wave plate is revolved and is turn 90 degrees, therefore by with the combination of polarized light diffraction element, optical characteristics such as can control the generation of the diffraction light that depends on the polarization direction and do not produce.
Make as phase retardation plate of the present invention under the situation of quarter wave plate, can give full play to for the light of wide wavelength region may the function that turn 90 degrees is revolved in the polarization direction.
In addition, phase retardation plate of the present invention also can use separately, but better is other optical element stacked use used with optical-head apparatus.By this, can realize the minimizing of number of components, the miniaturization of optical-head apparatus, the simplification of optical-head apparatus assembling procedure.As with the optical element of the stacked use of phase retardation plate, can exemplify the light of diffraction grating that 3 light beams use, the specific wavelength among the control multi-wavelength the opening limiting element, proofread and correct the aberration correcting element of the corrugated aberration that is produced etc.
In addition, if phase retardation plate of the present invention is used to have the optical-head apparatus of optical element of the difference of the characteristic that is produced by polarized light of utilizing polarized light diffraction element etc., then effect is good especially, also is suitable for the parts that requirement miniaturization and light-weighted optical-head apparatus are used.
Formation when optical anisotropic material of the present invention is used for the polarized light diffraction element is as follows usually.
At first, the polarized light diffraction element possesses the diffraction grating zone of the incident light of diffraction specific polarization state.This diffraction grating zone possesses the 1st member that is formed by the 1st material and the 2nd member that is formed by the 2nd material, and above-mentioned the 1st member is different for the specific refractory power of the incident light of above-mentioned specific polarization state with above-mentioned the 2nd member.In addition, above-mentioned the 1st member and above-mentioned the 2nd member with the spacing of regulation with the state configuration that is connected alternate with each other.Among the present invention, the 1st material uses optical anisotropic material of the present invention.
Here, the 1st material material not necessarily different with the 2nd material.But owing to the equal reason of the differently-oriented directivity of the material in each member, the 1st member is necessary different for the specific refractory power of the incident light of above-mentioned specific polarization state with the 2nd member.Making method as such polarized light diffraction element for example can exemplify following method.
(method 1)
Present method is, have electrode such as the ITO that forms pattern and carrying out clamping polymerizable liquid crystal compound of the present invention between a pair of substrate of orientation process towards prescribed direction, apply voltage by counter electrode, in polymerizable liquid crystal compound, form 2 kinds of zones with different orientation direction, after these 2 kinds of zones are staggered with the spacing of stipulating, carry out polymerization.Under this situation, above-mentioned the 1st member, the 2nd member are all formed by optical anisotropic material of the present invention, but because the state of orientation difference, for the specific refractory power difference of incident light, thereby can form the diffraction grating zone between each member.
(method 2)
Present method is, coating polymerizable liquid crystal compound of the present invention on the substrate that has carried out orientation process towards prescribed direction, make its polymerization and make optical anisotropic material, and form concavo-convex optical grating construction on the surface of this optical anisotropic material, fill optical isotropy material (with reference to Japanese patent laid-open 11-211905 communique etc.) at the grating recess.Under this situation, the formation of the polymerization of polymerizable liquid crystal compound of the present invention and concavo-convex raster shape can successively be carried out in any order.In addition, also can under the state of clamping polymerizable liquid crystal compound between two relative substrates, carry out polyreaction, peel off and form concavo-convex optical grating construction behind the substrate.
(method 3)
Present method is, after the surface of optical isotropy material forms concavo-convex optical grating construction, fills polymerizable liquid crystal compound of the present invention at the grating recess, carries out polymerization.
Here, concavo-convex optical grating construction can have the formation such as pressing mode of the mould of raster shape by adopting photolithographic etching method, dry etching method, employing.
The grating height of the diffraction grating in the polarized light diffraction element of the present invention better is 1～40 μ m, is more preferably 2～20 μ m.If the grating height in this scope, then can easily be made the polarized light diffraction element.In addition, polarized light diffraction element of the present invention can be made and has the polarized light diffraction element of diffraction efficiency arbitrarily by easily changing the grating height.
In addition, can be undertaken by methods such as spin coatings to the polymerizable liquid crystal compound of the grating recess of this optical grating construction or the filling of optical isotropy material (for example acrylic resin of photo-polymerization type or redix etc.).In addition, substrate itself exists under the concavo-convex situation, orientational disorder does not take place when polymerization is filled, and better is to use the substrate of having implemented friction treatment.
In addition, as polarized light diffraction element of the present invention, better be to have concavo-convex optical grating construction on the surface of optical anisotropic material, fill the ordinary refraction index n that has with above-mentioned optical anisotropic material at the recess at least of the jog of this optical grating construction
oThe refractive index n that equates
sThe polarized light diffraction element that forms of optical isotropy material.Such polarized light diffraction element can be made by above-mentioned method 2 or method 3.
Has ordinary refraction index n with optical anisotropic material of the present invention by filling like this
oThe refractive index n that equates
sThe optical isotropy material and the polarized light diffraction element according to the polarization direction of transmitted light, the situation and the inoperative situation of the effect of diffraction grating appears playing.
That is, fill the ordinary refraction index n that has with optical anisotropic material of the present invention at recess
oThe refractive index n that equates
sThe situation of optical isotropy material under, rectilinearly polarized light when producing the direction incident polarization optical diffraction element of ordinary refraction index, is not had refringence between optical anisotropic material and the optical isotropy material, do not produce diffracting effect.On the contrary, along producing when being the direction incident polarization optical diffraction element of unusual optical index of an angle of 90 degrees with this direction, there is refringence in rectilinearly polarized light between optical anisotropic material and the optical isotropy material, the generation diffracting effect.
Polarized light diffraction element of the present invention follows the decline of phase differential of the increase of light wavelength to be inhibited, and this is good on the one hand so depend on wavelength hardly in diffraction efficiency.
In addition, use optical anisotropic material of the present invention to be produced under the situation of the polarized light diffraction element that uses in certain wavelength region may, this material better is to be 0 and for the big material of the anisotropic value of specific refractory power of the light of other wavelength with respect to the anisotropic value of the specific refractory power of the light of the specific wavelength among the used multi-wavelength.By this, by the optical isotropy material that combination has suitable specific refractory power, can make the Wavelength-selective polarization hologram that except that the polarized light selectivity, also has wavelength selectivity concurrently.
In recent years, carry DVD with in semiconductor laser, the various optical-head apparatus of CD, can write down or reproduce the optical-head apparatus quilt commercialization gradually of multi-wavelength's exchange of the information that is write down in the CDs such as DVD, CD as the different optical recording medium of specification with semiconductor laser and blue-light semiconductor laser apparatus.
In this optical-head apparatus,, need give the wideband phase retardation plate of certain phase difference to multi-wavelength's laser for the phase state of modulated laser.In addition, in this optical-head apparatus,, require the light receiving element universalization that multi-wavelength's light is used for the minimizing of component count and the simplification of signal processing.For example, in order to detect optical signal with common light receiving element for the light of 2～3 different wavelength of the optical recording disk (HD DVD, BD), DVD and the CD that use blue laser, need be at suitable 2～3 the different polarized light diffraction elements of grating cycle of design of each wavelength.
If adopt phase retardation plate of the present invention and polarized light diffraction element, then can be applicable to the optical-head apparatus of the light that uses the multi-wavelength with 1 phase retardation plate, perhaps can be with 1 diffraction element light of diffraction multi-wavelength efficiently.Optical-head apparatus can adopt for example following form.
At first, optical-head apparatus possess the straight line polarising laser of the wavelength of outgoing respectively more than 2 kinds the semiconductor laser more than 2, will be from the above-mentioned laser convergence of above-mentioned semiconductor laser outgoing in the optical recording medium object lens, be disposed at the phase retardation plate of the phase state of the above-mentioned laser of control between above-mentioned semiconductor laser and the above-mentioned object lens.Wherein, above-mentioned phase retardation plate uses phase retardation plate of the present invention.
In addition, optical-head apparatus possess the semiconductor laser more than 2 of the straight line polarising laser of the wavelength of outgoing respectively more than 2 kinds, the polarisation of light optical diffraction element that above-mentioned laser convergence is reflected by optical recording medium in optical recording medium object lens, diffraction, the photodetector that detects diffracted emergent light.Wherein, above-mentioned polarized light diffraction element uses polarized light diffraction element of the present invention.
Use the concise and to the point side elevational view of an example of the optical-head apparatus of phase retardation plate of the present invention and polarized light diffraction element to be shown in Fig. 3.In this optical-head apparatus, respectively from the wavelength X of semiconductor laser 301 and 302 outgoing
1And λ
2Rectilinearly polarized light pass through reflected wavelength lambda
2Light and make wavelength X
1The light transmissive ripple prism 308 of closing closed ripple, through collimating lens 310 be held polarized light diffraction element 311, wideband phase retardation plate 312, the object lens 313 of actuator 314, understood coalescence and shone in information recording surface as the CD 315 of optical recording medium.The Returning beam from CD 315 reflections that comprises the information of the pit that is formed at information recording surface passes through each path along opposite direction.
Here, wideband phase retardation plate 312 is formed by optical anisotropic material of the present invention, for wavelength X
1And λ
2In any light all play the effect of quarter wave plate.In addition, polarized light diffraction element 311 also adopts optical anisotropic material of the present invention, therefore for wavelength X
1And λ
2In any light all have enough diffraction efficiencies.
That is, from as above-mentioned wavelength X
2The polarization direction of rectilinearly polarized light of light beam of semiconductor laser 302 outgoing of light source be concentrated in the direction that does not produce diffraction, wavelength X by polarized light diffraction element 311
2Light beam in penetrating the path, be not polarized optical diffraction element 311 reflections, transmission and incide wideband phase retardation plate 312 straight produces the phase differential of 1/4 λ, is converted into circularly polarized light, shines on the CD.In the return path, the Returning beam that is reflected by information recording surface and form the circularly polarized light of counter-rotating be converted into by wideband phase retardation plate 312 and incident polarization optical diffraction element 311 before vertical rectilinearly polarized lights, so be polarized optical diffraction element 311 diffraction, pass through collimating lens 310, close ripple prism 308, be imported into photodetector 305, the information that is recorded in CD 315 is read out.
In addition, for wavelength X
1 Close ripple prism 308 from the straight line polarising laser-transmitting of semiconductor laser 301 outgoing, through collimating lens 310 and the polarized light diffraction element 311, wideband phase retardation plate 312, the object lens 313 that are held in actuator 314, being understood coalescence shines in CD 315.Wavelength X
1Light beam and wavelength X
2Light beam same, produce the phase differential of 1/4 λ by wideband phase retardation plate 312, be converted into circularly polarized light, shine on the CD, so in penetrating the path, be converted into and incident polarization optical diffraction element 311 preceding vertical rectilinearly polarized lights by wideband phase retardation plate 312.In addition, with wavelength X
2Light beam similarly, be polarized optical diffraction element 311 diffraction, through collimating lens 310, close ripple prism 308, be imported into photodetector 304, the information that is recorded in CD 315 is read out.
Keep straight in the fused rings of compound of the present invention direction, be that the conjugate length of molecular long axis direction is short, therefore the photostabilization for short wavelength's light improves, and picks up the optical element of usefulness so also can be used for the light that blue laser uses well.
More than, the optical element that light is picked up usefulness is illustrated, but the present invention is not limited thereto, also can be used as other optical field, the optical element used etc. of communication etc. for example.
Embodiment
Below, exemplify embodiment, the present invention is carried out more specific description.
Synthesizing of (embodiment 1) compound (1A)
The synthesis example of (routine 1-1) compound (7)
With the frozen water refrigerative simultaneously, 1,5-dihydroxy naphthlene (32g, 0.2 mole), tetrahydrofuran (THF) (THF) (160mL) and in the mixture of triethylamine (21.3g, 0.21 mole) with 1 hour adding acrylate chloride (19g, 0.21 mole).Therebetween, the vigorous stirring reaction soln, temperature of reaction remains on below 20 ℃.Stir after 12 hours, leave standstill, carry out filtration under diminished pressure, filtrate decompression is concentrated.
Then, add methylene dichloride (100mL) in concentrated solution, cooling is left standstill.The solid that filtering separation is separated out concentrates filtrate decompression.Add methylene dichloride (50mL) in the residue after concentrating, carry out column chromatography (weighting agent: alkali alumina, expansion solvent: methylene dichloride).Affirmation after the outflow of 5-two propylene acyloxy naphthalenes, is taken out the alkali alumina in the post as 1 of by product, stirs to wherein adding 5% hydrochloric acid (400mL) and methylene dichloride (200mL).Behind the filtration under diminished pressure, separate organic layer, the washing back adds anhydrous magnesium sulfate drying.Then, by filtrate decompression is concentrated, obtain compound (7) (2.38g) (yield 5.5%).
The synthesis example of (routine 1-2) compound (1A)
Anti--4-n-butyl cyclohexane carboxylic acid (5.0g, 0.027 mole) is dissolved in THF (150mL), adds triethylamine (5.5g, 0.055 mole) and methylsulfonyl chloride (3.15g, 0.027 mole) ,-25 ℃ of stirrings 1 hour.In this mixing solutions, add compound (7) (5.35g, 0.025 mole) and the 4-dimethylaminopyridine (0.61g, 0.005 mole) that obtains among the routine 1-1, stirred 1 hour at-10 ℃.
Then, reaction soln is cleaned with 10% sodium bicarbonate aqueous solution and water, use anhydrous sodium sulfate drying, decompression concentrates down.Residue after concentrating is carried out silica gel column chromatography (launch solvent: methylene dichloride), obtain containing the part of compound (1A).With this partial concentration, the mixed solvent with hexane and toluene carries out recrystallization again, obtains the powder crystallization (2.96g) of compound (1A).Yield is 31.2%.
Compound (1A)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.91 (3H, t), 1.07 (1H, m), 1.31 (8H, m), 1.67 (2H, m), 1.92 (2H, m), 2.26 (2H, m), 2.66 (1H, m), 6.13 (1H, d), 6.48 (1H, m), 6.71 (1H, d), 7.25 (2H, m), 7.48 (2H, d), 7.76 (2H, t).
Under polarizing microscope, compound (1A) is observed, the result when heating up in 78 ℃ be isotropic liquid from crystalline transition, do not have liquid crystal liquid crystal property so confirm compound (1A).The infrared absorption spectrum of compound (1A) (KBr sheet) is shown in Fig. 4.
Synthesizing of (embodiment 2) compounds (1B)
Except will anti--4-n-butyl cyclohexane carboxylic acid change to instead-4-n-pentyl hexahydrobenzoic acid (5.5g, 0.027 mole) in addition, similarly operate with example 1, obtain compound (1B) (5.3g).Yield is 53.7%.
Compound (1B)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.90 (3H, t), 1.02 (1H, m), 1.30 (10H, m), 1.67 (2H, m), 1.91 (2H, m), 2.27 (2H, m), 2.65 (1H, m), 6.08 (1H, t), 6.45 (1H, m), 6.69 (1H, d), 7.25 (2H, m), 7.49 (2H, m), 7.76 (2H, m).
Under polarizing microscope, compound (1B) is observed, the result when heating up in 85.1 ℃ be isotropic liquid from crystalline transition, when cooling, change nematic phase into from isotropic liquid in 60.7 ℃, have liquid crystal liquid crystal property so confirm compound (1B).The infrared absorption spectrum of compound (1B) (KBr sheet) is shown in Fig. 5.
Synthesizing of (embodiment 3) compounds (1C)
Except will anti--4-n-butyl cyclohexane carboxylic acid change to instead-4-(instead-4-normal-butyl cyclohexyl) hexahydrobenzoic acid (7.3g, 0.027 mole) in addition, similarly operate with example 1, obtain compound (1C) (5.16g).Yield is 44.6%.
Compound (1C)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.91 (3H, t), 0.87～1.28 (14H, m), 1.62～1.92 (10H, m), 2.28 (1H, m), 2.65 (1H, m), 6.13 (1H, d), 6.49 (1H, m), 6.71 (1H, d), 7.26 (2H, m), 7.48 (2H, m), 7.77 (2H, t).
Under polarizing microscope, compound (1C) is observed, the result when heating up in 104 ℃ be nematic phase from crystalline transition, 193 ℃ is isotropic liquid from nematic Phase, has liquid crystal liquid crystal property so confirm compound (1C).The infrared absorption spectrum of compound (1C) (KBr sheet) is shown in Fig. 6.
Synthesizing of (embodiment 4) compounds (2B)
Add instead-1 in reactor, 4-cyclohexane dicarboxylic acid (17.2g), thionyl chloride (47.5g) and toluene (200mL) reflux and excessive thionyl chloride are heated up in a steamer with the toluene azeotropic after stirring, and obtain instead-1,4-hexanaphthene dicarboxyl acyl chlorides.
Then, obtain more than in reactor, adding anti--1,4-hexanaphthene dicarboxyl acyl chlorides and methylene dichloride (100mL) stir, and drip the solution that is formed by vinylformic acid-4-hydroxyl butyl ester (14.4g), pyridine (7.9g) and methylene dichloride (150mL), restir 1 hour simultaneously with the frozen water refrigerative.
Then, this reaction soln is added in the dilute hydrochloric acid, use dichloromethane extraction, heat up in a steamer after the washing and desolvate.Residue after will heating up in a steamer is handled with sodium bicarbonate aqueous solution, cleans with THF.Separate water layer, will be by be adjusted into the precipitate dichloromethane extraction that acidity is separated out with 5% aqueous hydrochloric acid.The washing dichloromethane layer is used dried over mgso, heats up in a steamer and desolvates, thereby obtain residue 1.
Then, in reactor, add above-mentioned residue 1 (6.5g), thionyl chloride (9.5g) and methylene dichloride (100mL), after the stirring that refluxes excessive thionyl chloride is heated up in a steamer with the methylene dichloride azeotropic, obtain residue 2.
Then, the residue 2 and the methylene dichloride (100mL) that obtain more than adding in reactor are dripping by 1 4-dihydroxy naphthlene-2 simultaneously with the frozen water refrigerative, the solution that 3-dintrile (2.1g), pyridine (1.5g) and tetrahydrofuran (THF) (150mL) form, restir 1 hour.
Then, reaction soln is added in the dilute hydrochloric acid, use dichloromethane extraction, the washing back is heated up in a steamer and is desolvated with after the dried over mgso.Residue after will heating up in a steamer is by column chromatography (weighting agent: silica gel, expansion solvent: THF) purifying.Concentrate the part that contains target compound,, obtain the powder crystallization of compound (2B) with the mixed solvent recrystallization of methylene dichloride and toluene.
Compound (2B)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 1.75 (16H, m), 2.37 (10H, m), 2.84 (2H, m), 4.19 (8H, m), 5.83 (2H, m), 6.12 (2H, m), 6.44 (2H, m), 7.84 (2H, m), 7.94 (2H, m).
Under polarizing microscope, compound (2B) is observed, the result when heating up in 176 ℃ be isotropic liquid from crystalline transition, do not have liquid crystal liquid crystal property so confirm compound (2B).The infrared absorption spectrum of compound (2B) (KBr sheet) is shown in Fig. 7.
Synthesizing of (embodiment 5) compounds (1U)
Synthesizing of (routine 5-1) compound (11)
In the there-necked flask that possesses thermometer and stirrer, add Na
2S
2O
4Water (87g) (800mL) solution, with adding 2 in 10 minutes, 3-two chloro-1, THF (800mL) solution of 4-naphthoquinones (22.7g, 0.1 mole) stirred 1 hour at 20 ℃.After the reaction, add methylene dichloride, wash 2 times.Organic layer by anhydrous magnesium sulfate drying, is removed solvent with rotatory evaporator.With residue recrystallization from toluene (250mL), obtain compound (11) (20.2g).Yield is 88%.The fusing point of compound (11) is 153.1 ℃.
Synthesizing of (routine 5-2) compound (12)
Then, to make anti--4-n-butyl cyclohexane carboxylic acid (12g, 0.065 mole) and thionyl chloride (15.5g) in methylene dichloride (150mL), react and must instead-dichloromethane solution of 4-n-butyl cyclohexane carboxyl acyl chloride is added drop-wise in THF (160mL) solution of the compound (11) (15g, 0.065 mole) that obtains among pyridine (5.5mL) and the routine 5-1.Dropping was being carried out with 30 minutes simultaneously with the ice bath refrigerative that remains in 5 ℃.After the pyridine hydrochloride of separating out removed, add methylene dichloride (300mL), use 5%NaHCO
3The aqueous solution cleans, and washes 2 times again.Use anhydrous magnesium sulfate drying, concentrate.Residue after concentrating is dissolved in methylene dichloride (100mL), carries out column chromatography (weighting material: neutral silica gel, expansion solvent: methylene dichloride), obtain compound (12) (2.3g).Yield is 9%.
The synthesis example of (routine 5-3) compound (1U)
With the mixture of the compound (12) (2.0g, 0.005 mole), THF (100mL) and the pyridine (0.625mL, 0.0073 mole) that obtain among the routine 5-2 simultaneously, with 30 minutes dropping acrylate chlorides (0.595mL, 0.0073 mole) with the frozen water refrigerative.Therebetween, the vigorous stirring reaction solution remains on temperature below 20 ℃.Stir after 12 hours, carry out filtration under diminished pressure, filtrate decompression is concentrated.Residue after concentrating (is launched solvent: methylene dichloride) behind the purifying, carry out recrystallization with the mixing solutions of hexane and toluene, obtain compound (1U) (0.2g) by silica gel column chromatography.Yield is 8.9%.
Compound (1U)
1H-N M R collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.91 (3H, t), 1.07 (2H, m), 1.31 (7H, m), 1.75 (2H, m), 1.94 (2H, m), 2.31 (2H, m), 2.74 (1H, m), 6.18 (1H, d), 6.50 (1H, m), 6.82 (1H, d), 7.55 (2H, m), 7.77 (2H, m).
Under polarizing microscope compound (1U) is observed, the result is isotropic liquid in 110 ℃ from crystalline transition when heating up.The infrared absorption spectrum of compound (1U) is shown in Fig. 8.
Synthesizing of (embodiment 6) compounds (1V)
Synthesizing of (routine 6-1) compound (13)
Except will anti--4-n-butyl cyclohexane carboxylic acid change to instead-4-n-pentyl hexahydrobenzoic acid (8.7g, 0.044 mole) in addition, similarly operate with routine 5-2, obtain compound (13) (3g).Yield is 16.6%.
Synthesizing of (routine 6-2) compound (1V)
Except compound (12) being changed to compound (13) (3g, 0.0065 mole) in addition, similarly operate with routine 5-3, obtain compound (1V) (0.5g).Yield is 17.1%.
Compound (1V)
1H-N M R collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.91 (3H, t), 1.27 (11H, m), 1.75 (2H, m), 1.94 (2H, m), 2.31 (2H, m), 2.74 (1H, m), 6.18 (1H, d), 6.50 (1H, m), 6.82 (1H, d), 7.55 (2H, m), 7.77 (2H, m).
Under polarizing microscope compound (1V) is observed, the result is isotropic liquid in 127 ℃ from crystalline transition when heating up.The infrared absorption spectrum of compound (1V) is shown in Fig. 9.
The making example (its 1) of (embodiment 7) phase retardation plate
The compound (1A), compound (1B) and the compound (1C) that obtain in the example 1～3 are mixed with 3: 4: 3 (mol ratio), obtain liquid-crystal composition A.Then, adding with respect to liquid-crystal composition A in liquid-crystal composition A is the Photoepolymerizationinitiater initiater (trade(brand)name: IRGACURE 907, Ciba corporate system) of 0.5 quality %, obtains liquid-crystal composition A1.
In the evaluation box of EHC corporate system, inject liquid-crystal composition A1 in 90 ℃, made its photopolymerization in 60 seconds, make phase retardation plate A in the ultraviolet ray of 25 ℃ of illumination wavelength 365nm.
With the glass razor demoulding of the face of phase retardation plate A, use mensuration machine (trade(brand)name: PRISMCOUPLER, METRICON corporate system) to measure specific refractory power for the laser of wavelength 412nm, 633nm, 780nm.
Calculate the specific refractory power anisotropy of phase retardation plate A by the specific refractory power of the direction parallel with the difference of the specific refractory power of the vertical direction of differently-oriented directivity with differently-oriented directivity.It the results are shown in Fig. 1.The anisotropic value of specific refractory power of affirmation phase retardation plate A increases with the increase of optical maser wavelength.
The making example (its 2) of (embodiment 8) phase retardation plate
With the compound (1A), compound (1B), compound (1C) and the compound (1U) that obtain in example 1～3 and 5 with 6: 8: 6: 5 (mol ratios) are mixed, and obtain liquid-crystal composition B.Then, adding with respect to liquid-crystal composition B in liquid-crystal composition B is the Photoepolymerizationinitiater initiater (trade(brand)name: IRGACURE 907, Ciba corporate system) of 0.5 quality %, obtains liquid-crystal composition B1.Use liquid-crystal composition B1, similarly make phase retardation plate B with example 7.
By the method same with example 7, for phase retardation plate B, measure specific refractory power for the laser of wavelength 412nm, 633nm, 780nm, calculate the anisotropic value of specific refractory power.The results are shown in Fig. 2.The anisotropic value of specific refractory power of affirmation phase retardation plate B increases with the increase of optical maser wavelength.
Synthesizing of (embodiment 9) compounds (1D)
Synthesizing of (routine 9-1) compound (14)
With the frozen water refrigerative simultaneously, 1, in the mixture of 4-dihydroxy naphthlene (32g, 0.2 mole), THF (160mL) and triethylamine (21.3g, 0.21 mole) with 1 hour adding acrylate chloride (19g, 0.21 mole).Therebetween, the vigorous stirring reaction soln, temperature of reaction remains on below 20 ℃.Stir after 12 hours, leave standstill, carry out filtration under diminished pressure.
Filtrate decompression is concentrated, in residue, add ethyl acetate (400mL), use 5%NaHCO
3The aqueous solution cleans, and washes 2 times again.Separate organic layer, use anhydrous magnesium sulfate drying, concentrate.Add methylene dichloride (400mL) in the residue after concentrating, cooling is left standstill.The solid that filtering separation is separated out, after filtrate decompression concentrated, (weighting agent: neutral silica gel, launch solvent: purifying methylene dichloride) obtained compound (14) (5.28g) by column chromatography.Yield is 12.4%.
The synthesis example of (routine 9-2) compound (1D)
To anti--4-(anti--4-normal-butyl cyclohexyl) hexahydrobenzoic acid (2.9g, 0.011 add methylene dichloride (40mL), methylsulfonyl chloride (11.9g, 0.1 mole) and dimethyl formamide (several) mole), at room temperature stir 2 hours after, underpressure distillation obtains white-yellowish solid.
With the frozen water refrigerative simultaneously, in the mixture of the compound that in routine 9-1, obtains (14) (2.1g, 0.01 mole), THF (30mL) and triethylamine (1.1g, 0.011 mole) with the mixture that added above-mentioned white-yellowish solid and THF (30mL) in 30 minutes.Therebetween, the vigorous stirring reaction soln, temperature of reaction remains on below 5 ℃.Stir after 3 hours, leave standstill, carry out filtration under diminished pressure.
Filtrate decompression is concentrated, in residue, add ethyl acetate (200mL) and make its dissolving, use 5%NaHCO
3The aqueous solution cleans, and washes 2 times again.Separate organic layer, use anhydrous magnesium sulfate drying, concentrate.Residue after concentrating is carried out column chromatography (weighting agent: neutral silica gel, expansion solvent: methylene dichloride), obtain containing the part of compound (1D).With this partial concentration, carry out recrystallization with ethyl acetate again, obtain the powder crystallization (2.66g) of compound (1D).Yield is 57.8%.
Compound (1D)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.89～1.28 (18H, m), 1.69～1.92 (8H, m), 2.30 (2H, m), 2.65 (1H, m), 6.12 (1H, d), 6.48 (1H, m), 6.73 (1H, d), 7.26 (2H, m), 7.54 (2H, m), 7.87 (2H, m).
Under polarizing microscope, compound (1D) is observed, the result when heating up in 118 ℃ be nematic phase from crystalline transition, so confirm to have liquid crystal liquid crystal property.Because thermopolymerization and unconfirmed to the phase transition temperature of isotropic phase.The infrared absorption spectrum of compound (1D) (KBr sheet) is shown in Figure 10.
Synthesizing of (embodiment 10) compounds (1W)
Except will anti--4-(anti--4-normal-butyl cyclohexyl) hexahydrobenzoic acid change to instead-4-n-butyl cyclohexane carboxylic acid (2.02g, 0.011 mole) in addition, similarly operate with routine 9-2, obtain compound (1W) (1.5g).Yield is 39.5%.
Compound (1W)
1H-NMR collection of illustrative plates (solvent: CDCl
3, interior mark: TMS) be δ (ppm): 0.91 (3H, t), 1.07 (2H, m), 1.30 (7H, m), 1.68 (2H, m), 1.93 (2H, m), 2.27 (2H, m), 2.67 (1H, m), 6.11 (1H, d), 6.47 (1H, m), 6.72 (1H, d), 7.25 (2H, m), 7.53 (2H, m), 7.87 (2H, m).
Under polarizing microscope compound (1W) is observed, the result is isotropic liquid in 88 ℃ from crystalline transition when heating up.The infrared absorption spectrum of compound (1W) (KBr sheet) is shown in Figure 11.
The making example (its 3) of (embodiment 11) phase retardation plate
The compound (1D) and the compound (1W) that obtain in example 9 and 10 are mixed with 5: 5 (mol ratio), obtain liquid-crystal composition C.Then, adding with respect to liquid-crystal composition C in liquid-crystal composition C is the Photoepolymerizationinitiater initiater (trade(brand)name: IRGACURE 907, Ciba corporate system) of 0.5 quality %, obtains liquid-crystal composition C1.Use liquid-crystal composition C1, similarly make phase retardation plate C with example 7.
For phase retardation plate C, the phase differential when measuring for wavelength 405nm, 660nm, 785nm.By with the value of this phase differential thickness (thickness of the optical anisotropic material after the polymerization), the anisotropic value of the specific refractory power when calculating each wavelength divided by phase retardation plate C.The results are shown in Figure 12.The anisotropic value of specific refractory power of affirmation phase retardation plate C increases with the increase of optical maser wavelength.
The possibility of utilizing on the industry
Polymerizable compound of the present invention can be used for the adjustment of the anisotropic wavelength dispersibility of specific refractory power.Therefore, will contain this polymerizable compound the polymerizable liquid crystal compound polymerization and optical anisotropic material can be used for optical elements such as phase retardation plate, polarized light diffraction element.By suitably adjusting wavelength dispersion, these optical elements can not be subjected to the polarized light diffraction element of wavelength affects as broadband wave plate or efficient, so can be used as the used optical element of optical-head apparatus of the continuous use multi-wavelength's who increases of demand laser in recent years.
In addition, quote the announcement of all the elements of Japanese patent application 2005-115886 number of filing an application on April 13rd, 2005 and Japanese patent application 2005-362891 number specification sheets, claims, accompanying drawing and the summary of filing an application on December 16th, 2005 here as specification sheets of the present invention.
Claims (13)
1. polymerizable liquid crystal compound, it is characterized in that, comprise and have mesomorphic unit and be polymerizable compound two terminal bonded 1 valency end groups of this mesomorphic unit, at least one side of this end group respectively with the 1 valency organic group at polymerizability position, described mesomorphic unit by at least one side's of following fused benzene rings base (A) associative key directly or be situated between with-OCO-basic as connecting or-COO-obtains in conjunction with 6 yuan of cyclic groups (B); Fused benzene rings base (A): at 1 and 4 or 5 naphthalene with associative key, two bases or at 1 or 9 and 4,5 or 10 anthracene two bases with associative key, 6 yuan of cyclic groups (B): 1,4-phenylene, anti--1, the 4-cyclohexylidene or by the group more than 2 that is selected from these groups directly or be situated between with connect base in conjunction with and the divalent group.
2. polymerizable liquid crystal compound as claimed in claim 1 is characterized in that, contains following formula (1) CH
2=CR
1-COO-J
1-(E
1-J
2)
n-W
1-J
3-M-R
2(1)
The polymerizable compound of expression, the R in the formula
1, R
2, n, J
1, J
2, J
3, E
1, W
1And the implication of M is as described below:
R
1: hydrogen atom or methyl, R
2: the alkyl of carbon number 2～8, n:0 or 1, J
1: singly-bound ,-(CH
2)
a-or-(CH
2)
bO-, a wherein and b are respectively 2～8 integer independently, J
2, J
3: respectively be independently singly-bound ,-OCO-or-COO-, E
1: 1,4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
1: naphthalene-1,4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,10-two bases, hydrogen atom in these groups can be replaced M: be selected from following formula (a)～(f) by chlorine atom, fluorine atom, methyl or cyano group
Arbitrary group of the group of expression.
3. polymerizable liquid crystal compound as claimed in claim 2 is characterized in that, contains M for being selected from following formula (a)～(e)
The polymerizable compound of arbitrary group of the group of expression.
4. polymerizable liquid crystal compound as claimed in claim 3 is characterized in that, contains M for anti--1,4-cyclohexylidene or anti-, the polymerizable compound of anti--4,4 '-two cyclohexylidenes.
5. polymerizable liquid crystal compound as claimed in claim 1 is characterized in that, contains following formula (2) CH
2=CR
3-COO-J
4-E
2-COO-W
2-OCO-E
3-J
5-OCO-CR
3=CH
2(2)
The polymerizable compound of expression, the R in the formula
3, J
4, J
5, E
2, E
3And W
2Implication as described below: R
2: hydrogen atom or methyl, J
4:-(CH
2)
tO-or-(CH
2)
uO-CO-, wherein, t and u are respectively 2～6 integer independently, J
5:-O (CH
2)
c-or-COO-(CH
2)
d-, wherein, c and d are respectively 2～6 integer independently, E
2, E
3: be respectively 1 independently, 4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
2: naphthalene-1,4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,1O-two bases, the hydrogen atom in these groups can be replaced by chlorine atom, fluorine atom, methyl or cyano group.
6. polymerizable liquid crystal compound is characterized in that, in the claim 1～5 content of each described polymerizable compound with respect to polymerizable liquid crystal compound more than 10 quality %.
7. optical anisotropic material is characterized in that, makes each described polymerizable liquid crystal compound polymerization in the claim 1～5 and gets.
8. optical anisotropic material as claimed in claim 7 is characterized in that, described material is the optics uniaxiality, as ordinary refraction index n
oWith unusual optical index n
eThe value of specific refractory power anisotropy Δ n of difference increase along with the increase of used light wavelength.
9. optical element is characterized in that, adopts claim 7 or 8 described optical anisotropic materials to form, and controls used polarisation of light light state and/or phase state.
10. phase retardation plate is characterized in that, adopts claim 7 or 8 described optical anisotropic materials to form.
11. polarized light diffraction element, it is the polarized light diffraction element that possesses the diffraction grating zone of diffraction incident light, it is characterized in that, aforementioned diffraction grating zone possesses the 1st member that is formed by the 1st material and the 2nd member that is formed by the 2nd material, aforementioned the 1st member is different at least a polarized light refractive index with aforementioned the 2nd member, aforementioned the 1st member and aforementioned the 2nd member are with the state configuration that is connected alternate with each other, and aforementioned the 1st material is claim 7 or 8 described optical anisotropic materials.
12. optical-head apparatus, it is by semiconductor laser, object lens, photodetector, is disposed at the optical-head apparatus that phase retardation plate between aforementioned object lens and the aforementioned lights detector and/or polarized light diffraction element constitute, it is characterized in that aforementioned phase retardation plate is that described phase retardation plate of claim 10 and/or aforementioned polarized light diffraction element are the described polarized light diffraction element of claim 11.
13. following formula (1) or (2)
CH
2＝CR
1-COO-J
1-(E
1-J
2)
n-W
1-J
3-M-R
2……(1)
CH
2＝CR
3-COO-J
4-E
2-COO-W
2-OCO-E
3-J
5-OCO-CR
3＝CH
2……(2)
The polymerizable compound of expression, the R in the formula
1, R
2, R
3, n, J
1, J
2, J
3, J
4, J
5, E
1, E
2, E
3, W
1, W
2And the implication of M is as described below:
R
1, R
3: be hydrogen atom or methyl independently respectively, R
2: the alkyl of carbon number 2～8, n:0 or 1, J
1: singly-bound ,-(CH
2)
a-or-(CH
2)
bO-, a wherein and b are respectively 2～8 integer independently, J
2, J
3: respectively be independently singly-bound ,-OCO-or-COO-, J
4:-(CH
2)
tO-or-(CH
2)
uO-CO-, wherein, t and u are respectively 2～6 integer independently, J
5:-O (CH
2)
c-or-COO-(CH
2)
d-, wherein, c and d are respectively 2～6 integer independently, E
1, E
2, E
3: be respectively 1 independently, 4-phenylene or anti--1, the 4-cyclohexylidene, the hydrogen atom in these groups can be replaced W by chlorine atom, fluorine atom, methyl or cyano group
1, W
2: be naphthalene-1 independently respectively, 4-two bases, naphthalene-1,5-two bases, anthracene-1,4-two bases, anthracene-1,5-two bases, anthracene-1,10-two bases, anthracene-4,9-two bases, anthracene-5,9-two bases or anthracene-9,10-two bases, hydrogen atom in these groups can be replaced M: be selected from following formula (a)～(f) by chlorine atom, fluorine atom, methyl or cyano group
Arbitrary group of the group of expression.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP115886/2005 | 2005-04-13 | ||
| JP2005115886 | 2005-04-13 | ||
| JP362891/2005 | 2005-12-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101155897A true CN101155897A (en) | 2008-04-02 |
Family
ID=39256900
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102076721B (en) * | 2008-06-30 | 2013-04-24 | 日本瑞翁株式会社 | Polymerizable liquid crystal compounds, polymerizable liquid crystal compositions, liquid crystal polymers and optically anisotropic materials |
| CN102046586B (en) * | 2008-06-06 | 2013-12-04 | 旭硝子株式会社 | Liquid crystal compound, polymerizable liquid crystal composition, optically anisotropic material, optical element and optical information recording/playback device |
| CN102046584B (en) * | 2008-05-30 | 2014-01-22 | 旭硝子株式会社 | Compound, polymerizable liquid crystalline composition, optical element, and optical information recording/reproduction device |
| CN106433690A (en) * | 2015-08-06 | 2017-02-22 | 旭硝子株式会社 | Liquid crystal composition and liquid crystal optical device |
| CN106855646A (en) * | 2015-12-09 | 2017-06-16 | 财团法人工业技术研究院 | Wide wave-domain phase delay film and wide wave-domain circular polarizer using same |
-
2006
- 2006-04-12 CN CNA2006800117216A patent/CN101155897A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046584B (en) * | 2008-05-30 | 2014-01-22 | 旭硝子株式会社 | Compound, polymerizable liquid crystalline composition, optical element, and optical information recording/reproduction device |
| CN102046586B (en) * | 2008-06-06 | 2013-12-04 | 旭硝子株式会社 | Liquid crystal compound, polymerizable liquid crystal composition, optically anisotropic material, optical element and optical information recording/playback device |
| CN102076721B (en) * | 2008-06-30 | 2013-04-24 | 日本瑞翁株式会社 | Polymerizable liquid crystal compounds, polymerizable liquid crystal compositions, liquid crystal polymers and optically anisotropic materials |
| CN106433690A (en) * | 2015-08-06 | 2017-02-22 | 旭硝子株式会社 | Liquid crystal composition and liquid crystal optical device |
| CN106855646A (en) * | 2015-12-09 | 2017-06-16 | 财团法人工业技术研究院 | Wide wave-domain phase delay film and wide wave-domain circular polarizer using same |
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Application publication date: 20080402 |