WO2013018526A1 - Procédé d'ajustement de la dispersion des longueurs d'ondes d'un isomère optique et composition polymérisable - Google Patents

Procédé d'ajustement de la dispersion des longueurs d'ondes d'un isomère optique et composition polymérisable Download PDF

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WO2013018526A1
WO2013018526A1 PCT/JP2012/067906 JP2012067906W WO2013018526A1 WO 2013018526 A1 WO2013018526 A1 WO 2013018526A1 JP 2012067906 W JP2012067906 W JP 2012067906W WO 2013018526 A1 WO2013018526 A1 WO 2013018526A1
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group
carbon atoms
compound
aromatic
ring
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PCT/JP2012/067906
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坂本　圭
久美 奥山
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日本ゼオン株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

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  • the present invention provides the specific polymerizable compound in the polymerizable composition and other A method for adjusting the wavelength dispersion of an optical anisotropic body, and a polymerizable composition suitable for carrying out this method, wherein an optical anisotropic body having desired wavelength dispersion characteristics is obtained by adjusting a blending ratio with the polymerizable compound.
  • Flat panel display is widely used as an excellent display device because high-definition display is possible by using optical anisotropic bodies (optically anisotropic films) such as polarizing plates and retardation plates.
  • optical anisotropic bodies such as polarizing plates and retardation plates.
  • As the retardation plate a thin plate made of an inorganic material such as calcite, mica, quartz, or a stretched polymer film having high intrinsic birefringence is known.
  • These types of retardation plates include a 1 ⁇ 4 wavelength plate that converts linearly polarized light into circularly polarized light, and a 1 ⁇ 2 wavelength plate that converts the polarization vibration plane of linearly polarized light by 90 degrees.
  • a conventional retardation plate can accurately convert a specific monochromatic light into a phase difference of 1 / 4 ⁇ or 1 / 2 ⁇ of a light wavelength, but it is a composite wave in which light in the visible light range is mixed.
  • the polarized light output through the retardation plate may be converted into colored polarized light. This originates in the material which comprises a phase difference plate having wavelength dispersion about a phase difference.
  • JP 2002-267838 A JP 2003-160540 A (US20030102458A1) JP 2005-208414 A JP 2005-208415 A JP 2005-208416 A Japanese Patent Laying-Open No. 2005-289980 (US20070176145A1) JP 2006-330710 A (US20090072194A1) JP 2009-179563 A (US200901189120A1) JP 2010-31223 A JP 2011-6360 A JP 2011-6361 A JP 2011-42606 A JP 2010-537954 A (US201100201920A1) Japanese Translation of PCT International Publication No. 2010-537955 (US2013012711A1) International Publication No. 2006/052001 (US20070298191A1) US Pat. No.
  • the present invention has been made in view of the above-described prior art, and in producing an optical anisotropic body using a polymerizable composition containing a specific polymerizable compound and another polymerizable compound, the polymerization is performed.
  • the method for adjusting the wavelength dispersion of an optical anisotropic body which obtains an optical anisotropic body having desired wavelength dispersion characteristics by adjusting the blending ratio of a specific polymerizable compound and another polymerizable compound in the polymerizable composition, And it aims at providing the polymeric composition suitable for implementation of this method.
  • the inventors of the present invention optically used a polymerizable composition containing a polymerizable compound (I) represented by the following formula (I) and another polymerizable compound.
  • a polymerizable compound (I) represented by the following formula (I) and another polymerizable compound.
  • an optical anisotropic body having a desired wavelength dispersion characteristic is obtained by adjusting the blending ratio of the polymerizable compound (I) and the other polymerizable compound in the polymerizable composition. (That is, the wavelength dispersion characteristic of the obtained optical anisotropic body can be easily and easily adjusted), and the present invention has been completed.
  • the present invention there are provided (1) to (8) methods for adjusting the wavelength dispersion of optically anisotropic bodies and (9) a polymerizable composition.
  • (1) In producing an optical anisotropic body using a polymerizable composition containing a polymerizable compound (I) represented by the following formula (I) and another polymerizable compound, the polymerizable composition
  • Y 1 to Y 6 are each independently a chemical single bond, —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, — OC ( ⁇ O) —O—, —NR 1 —C ( ⁇ O) —, —C ( ⁇ O) —NR 1 —, —O—C ( ⁇ O) —NR 1 —, —NR 1 — C ( ⁇ O) —O—, —NR 1 —C ( ⁇ O) —NR 1 —, or —NR 1 —O— is represented.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • G 1 and G 2 each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent
  • the aliphatic group includes —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —NR 2 —C ( ⁇ O) —, —C ( ⁇ O) — NR 2 —, —NR 2 —, or —C ( ⁇ O) — may be present.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ].
  • a x and A y may be combined to form a ring.
  • a 1 represents a trivalent aromatic group which may have a substituent.
  • a 2 and A 3 each independently represents a divalent aromatic group having 4 to 30 carbon atoms which may have a substituent.
  • Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • the optically anisotropic compound according to (1) wherein the polymerizable compound (I) is a compound in which the total number of ⁇ electrons contained in A x and A y is 4 or more and 24 or less in the formula (I). Method for adjusting chromatic dispersion of body.
  • the polymerizable compound (I) is a trivalent benzene ring group or a trivalent naphthalene ring group, wherein A 1 may have a substituent in the formula (I), and A 2 and A 3 are each independently a phenylene group or naphthylene group compound which may have a substituent, The method for adjusting wavelength dispersion of an optical anisotropic body according to (1) or (2) .
  • Y 1 to Y 6 are each independently a chemical single bond, —O—, —O—C ( ⁇ O) — , —C ( ⁇ O) —O—, or —O—C ( ⁇ O) —O—, which is a compound of (1) to (3), Method.
  • the polymerizable compound (I) is a divalent aliphatic having 1 to 12 carbon atoms in which G 1 and G 2 in the formula (I) each independently have a substituent.
  • a group [the aliphatic group may intervene —O—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O— or —C ( ⁇ O) —.
  • the method for adjusting wavelength dispersion of an optical anisotropic body according to any one of (1) to (5) which is a compound of (7)
  • the polymerizable compound (I) is a compound having a divalent alkylene group having 1 to 12 carbon atoms, wherein G 1 and G 2 in the formula (I) are each independently (5)
  • the method for adjusting wavelength dispersion of an optical anisotropic body according to any one of (5) is a compound having a divalent alkylene group having 1 to 12 carbon atoms, wherein G 1 and G 2 in the formula (I) are each independently (5).
  • Y 11 to Y 16 are each independently a chemical single bond, —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, — OC ( ⁇ O) —O—, —NR 11 —C ( ⁇ O) —, —C ( ⁇ O) —NR 11 —, —O—C ( ⁇ O) —NR 11 —, —NR 11 —.
  • C ( ⁇ O) —O—, —NR 11 —C ( ⁇ O) —NR 11 —, —O—NR 11 —, or —NR 11 —O— is represented.
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • G 11 and G 12 each independently represent a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent
  • the aliphatic group includes —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —NR 12 —C ( ⁇ O) —, —C ( ⁇ O) — NR 12 —, —NR 12 —, or —C ( ⁇ O) — may be present.
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ].
  • Z 11 and Z 12 each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
  • a a represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring
  • a b has a hydrogen atom and a substituent. It represents an optionally substituted alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the aromatic ring within A a and A b may have a substituent.
  • a a and A b may be combined to form a ring.
  • a 11 represents a trivalent aromatic group which may have a substituent.
  • a 12 and A 13 each independently represents a divalent aromatic group having 4 to 30 carbon atoms which may have a substituent.
  • Q 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • a polymerizable composition comprising at least one polymerizable compound (I) according to (1) and at least one polymerizable compound (II) according to (8).
  • the wavelength dispersion characteristics of the optical anisotropic body can be easily and highly controlled, and it is possible to meet various chromatic dispersion characteristic requests from customers. it can.
  • an optical anisotropic body in which the wavelength dispersion characteristics of the optical anisotropic body are controlled can be obtained easily and efficiently, and an optical film satisfying in terms of performance can be produced easily and efficiently.
  • it can be suitably used as a method for adjusting the wavelength dispersion of an optical anisotropic body having reverse wavelength dispersion.
  • the polymerizable composition of the present invention can be used for the wavelength dispersion adjusting method of the present invention, and can be particularly suitably used for the reverse wavelength dispersion adjusting method.
  • the wavelength dispersion adjusting method of the present invention it is possible to easily form an optical film that is capable of uniform polarization conversion in a wide wavelength range and that is satisfactory in terms of performance.
  • an antireflection film can be produced by combining with a polarizing plate, and industrially, for example, it can be suitably used for antireflection of touch panels and organic electroluminescent elements.
  • the method for adjusting the wavelength dispersion of the optical anisotropic body of the present invention when producing an optical anisotropic body using a polymerizable composition containing the polymerizable compound (I) and another polymerizable compound, By adjusting the blending ratio of the polymerizable compound (I) and the other polymerizable compound, the wavelength dispersibility of the obtained optical anisotropic body can be easily and easily adjusted.
  • optically anisotropic substances obtained using a polymerizable composition containing a polymerizable compound (I) and not containing other polymerizable compounds often exhibit reverse wavelength dispersion, and other polymerizable compounds
  • Many optical anisotropic bodies obtained using a polymerizable composition containing and not containing a polymerizable compound (I) exhibit positive wavelength dispersion or flat wavelength dispersion.
  • reverse wavelength dispersion specifically means a wavelength dispersion characteristic satisfying a relationship of (phase difference at a wavelength of 450 nm) ⁇ (phase difference at a wavelength of 550 nm) ⁇ (phase difference at a wavelength of 650 nm).
  • “Positive wavelength dispersion” means wavelength dispersion characteristics satisfying the relationship of (phase difference at wavelength 450 nm)> (phase difference at wavelength 550 nm)> (phase difference at wavelength 650 nm).
  • flat wavelength dispersion means wavelength dispersion characteristics satisfying the relationship of (phase difference at a wavelength of 450 nm) ⁇ (phase difference at a wavelength of 550 nm) ⁇ (phase difference at a wavelength of 650 nm).
  • a polymerizable composition containing a polymerizable compound (I) that gives an optical anisotropic body exhibiting reverse wavelength dispersion, and another polymerizable compound that gives an optical anisotropic body showing flat wavelength dispersion The blending ratio of the polymerizable compound (I) and the other polymerizable compound is changed between 0: 100 and 100: 0 in a weight ratio of [polymerizable compound (I)] :( other polymerizable compound).
  • the wavelength dispersion characteristic of the obtained optical anisotropic body can be adjusted.
  • the horizontal axis indicates the measurement wavelength (nm)
  • the vertical axis indicates the phase difference (Re (nm)) at the measurement wavelength.
  • the graph shown in FIG. 1 will be described in detail in an example section described later.
  • the present invention it is desirable to adjust the blending ratio of the polymerizable compound (I) and the other polymerizable compound in the polymerizable composition that is a raw material for producing the optical anisotropic body. It is possible to obtain an optical anisotropic body having the wavelength dispersion characteristics [that is, the wavelength dispersion characteristics of the obtained optical anisotropic body can be easily adjusted (controlled). ].
  • the curve shown in FIG. 1 shifts in the vertical direction as a whole when the thickness of the optical anisotropic body in the measurement direction changes. That is, when the thickness of the optical anisotropic body in the measurement direction is increased, the value of Re (nm) at the measurement wavelength is increased, and when the thickness is decreased, the value of Re (nm) at the measurement wavelength is decreased. Therefore, the value of Re (nm) at the measurement wavelength can be adjusted by adjusting the thickness of the optical anisotropic body.
  • the polymerizable compound (I) used in the present invention is a compound represented by the formula (I).
  • Y 1 to Y 6 are each independently a chemical single bond, —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms of R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n- A hexyl group etc. are mentioned.
  • Y 1 to Y 6 are each independently a chemical single bond, —O—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, or —O.
  • G 1 and G 2 each independently represent a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent.
  • the divalent aliphatic group having 1 to 20 carbon atoms include a divalent aliphatic group having 1 to 20 carbon atoms having a chain structure; a divalent aliphatic having 3 to 20 carbon atoms having an alicyclic structure And a combination of a divalent aliphatic group having 1 to 20 carbon atoms having a chain structure and a divalent aliphatic group having 3 to 20 carbon atoms having an alicyclic structure.
  • Examples of the divalent aliphatic group having 1 to 20 carbon atoms having a chain structure include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octane group,
  • An alkylene group having 1 to 20 carbon atoms such as a methylene group, a nonamethylene group, a decamethylene group; an alkenylene group having 2 to 20 carbon atoms such as a vinylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, or a hexadienylene group;
  • Examples of the divalent aliphatic group having 3 to 20 carbon atoms having an alicyclic structure include a cycloalkanediyl group having 3 to 20 carbon atoms, a divalent alicyclic condensed ring group having 7 to 20 carbon atoms, and And combinations thereof.
  • Examples of the cycloalkanediyl group having 3 to 20 carbon atoms include cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecandidiyl group, and cyclododecandiyl group. , Cyclotetradecandiyl group, cycloeicosanediyl group and the like.
  • Examples of the divalent alicyclic fused ring group having 7 to 20 carbon atoms include a bicyclo [2.2.1] heptanediyl group, an adamantanediyl group, and a decalindiyl group.
  • Examples of combinations of a divalent aliphatic group having 1 to 20 carbon atoms having a chain structure and a divalent aliphatic group having 3 to 20 carbon atoms having an alicyclic structure include the following.
  • Examples of the substituent of the divalent aliphatic group having 1 to 20 carbon atoms having the chain structure include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; carbon numbers such as methyl group and ethyl group 1 to 6 alkyl groups; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. And an alkoxy group having 1 to 6 carbon atoms. Among these, a fluorine atom, a methoxy group, and an ethoxy group are preferable.
  • Examples of the substituent of the divalent aliphatic group having 3 to 20 carbon atoms having the alicyclic structure include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; carbon such as methyl group and ethyl group An alkyl group of 1 to 6; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. And an alkoxy group having 1 to 6 carbon atoms. Among these, a fluorine atom, a methoxy group, and an ethoxy group are preferable.
  • the aliphatic groups of G 1 and G 2 include —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O ) —O—, —NR 2 —C ( ⁇ O) —, —C ( ⁇ O) —NR 2 —, —NR 2 —, or —C ( ⁇ O) — may be present.
  • the case where two or more of —O— or —S— are adjacent to each other is excluded.
  • —O—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, or —C ( ⁇ O) — is preferable.
  • R 2 represents the same hydrogen atom or alkyl group having 1 to 6 carbon atoms as R 1, and is preferably a hydrogen atom or a methyl group.
  • G 1 and G 2 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, etc., from the viewpoint of better expressing the desired effect of the present invention.
  • a divalent aliphatic group having 1 to 20 carbon atoms having a chain structure such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, etc.
  • an alkylene group having 1 to 12 carbon atoms is more preferable, and a tetramethylene group [— (CH 2 ) 4 —] and a hexamethylene group [— (CH 2 ) 6 —] are particularly preferable.
  • Z 1 and Z 2 each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
  • the alkenyl group preferably has 2 to 6 carbon atoms.
  • Examples of the halogen atom that is a substituent of the alkenyl group of Z 1 and Z 2 include a fluorine atom, a chlorine atom, a bromine atom, and the like, and a chlorine atom is preferable.
  • Z 1 and Z 2 include CH 2 ⁇ CH—, CH 2 ⁇ C (CH 3 ) —, CH 2 ⁇ CH—CH 2 —, CH 3 —CH ⁇ CH—, CH 2 ⁇ CH—CH. 2 —CH 2 —, CH 2 ⁇ C (CH 3 ) —CH 2 —CH 2 —, (CH 3 ) 2 C ⁇ CH—CH 2 —, (CH 3 ) 2 C ⁇ CH—CH 2 —CH 2 — CH 2 ⁇ C (Cl) —, CH 2 ⁇ C (CH 3 ) —CH 2 —, CH 3 —CH ⁇ CH—CH 2 — and the like.
  • CH 2 ⁇ CH—, CH 2 ⁇ C (CH 3 ) —, CH 2 Preferably, C (Cl) —, CH 2 ⁇ CH—CH 2 —, CH 2 ⁇ C (CH 3 ) —CH 2 —, or CH 2 ⁇ C (CH 3 ) —CH 2 —CH 2 — is preferred.
  • CH 2 ⁇ CH—, CH 2 ⁇ C (CH 3 ) —, or CH 2 ⁇ C (Cl) — is more preferable, and CH 2 ⁇ CH— is still more preferable.
  • a x represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the “aromatic ring” means a cyclic structure having a broad meaning of aromaticity according to the Huckle rule, that is, a cyclic conjugated structure having (4n + 2) ⁇ electrons, sulfur, oxygen, etc. represented by thiophene, furan, etc. This means that the lone pair of heteroatoms of the present invention participates in the ⁇ -electron system and exhibits aromaticity.
  • the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of A x may have a plurality of aromatic rings. And having an aromatic hydrocarbon ring and an aromatic heterocycle.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring.
  • aromatic heterocycle examples include 5-membered aromatic heterocycles such as pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring and thiazole ring; pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc. 6-membered aromatic heterocycles; condensed aromatic heterocycles such as benzimidazole ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, carbazole ring; and the like.
  • the aromatic ring of A x may have a substituent.
  • substituents include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and 2 to 6 carbon atoms such as vinyl group and allyl group.
  • An alkenyl group of 1 to 6 carbon atoms such as a trifluoromethyl group; an amino group; a substituted amino group such as a methylamino group, a dimethylamino group or an acetylamino group; a methoxy group, an ethoxy group or an isopropoxy group;
  • An alkoxy group having 1 to 6 carbon atoms such as: a nitro group; an aryl group such as a phenyl group or a naphthyl group; a —C ( ⁇ O) —OR group; an —SO 2 R group;
  • R represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • the aromatic ring within A x may have a plurality of identical or different substituents, bonded two adjacent substituents together may form a ring.
  • the ring formed may be monocyclic or condensed polycyclic.
  • the “carbon number” of the organic group having 2 to 30 carbon atoms in A x means the total number of carbon atoms in the whole organic group not including the carbon atom of the substituent (the same applies to A y described later). .
  • an aromatic hydrocarbon ring group As the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of A x , an aromatic hydrocarbon ring group; an aromatic heterocyclic ring Group: an alkyl group having 3 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group; from an aromatic hydrocarbon ring group and an aromatic heterocyclic group An alkenyl group having 4 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of: a carbon number having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group 4-30 alkynyl groups; and the like.
  • a y has a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms.
  • a y is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom.
  • alkyl group having 1 to 6 carbon atoms which may have a substituent of A y include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl.
  • substituent of the alkyl group having 1 to 6 carbon atoms which may have a substituent, a fluorine atom, a halogen atom such as a chlorine atom; a cyano group; a substituted amino group such as dimethylamino group; methoxy Alkoxy groups having 1 to 6 carbon atoms such as ethoxy, isopropoxy and the like; nitro groups; aryl groups such as phenyl and naphthyl groups; —C ( ⁇ O) —OR groups; —SO 2 R groups; Can be mentioned.
  • R represents the same meaning as described above.
  • Examples of the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring for A y are the same as those exemplified for A x above. Is mentioned.
  • aromatic ring of A x and A y are shown below.
  • a x, aromatic ring within A y is not intended to be limited to those shown below.
  • [-] represents a bond of an aromatic ring (the same applies hereinafter).
  • E represents NR 13 , an oxygen atom or a sulfur atom.
  • R 13 represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group.
  • X, Y and Z each independently represent NR 13 , oxygen atom, sulfur atom, —SO— or —SO 2 — (provided that oxygen atom, sulfur atom, —SO—, — Except when SO 2 -is adjacent to each other).
  • R 13 represents the same meaning as described above.
  • a x and A y may be combined to form a ring.
  • the unsaturated heterocyclic ring having 4 to 30 carbon atoms and the unsaturated carbocyclic ring having 6 to 30 carbon atoms are not particularly limited and may or may not have aromaticity.
  • the ring shown below is mentioned.
  • the ring shown below is the one in the formula (I)
  • X, Y and Z represent the same meaning as described above.
  • these rings may have a substituent.
  • substituents include a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a —C ( ⁇ O) —OR group, an —SO 2 R group, and the like. It is done.
  • R represents the same meaning as described above.
  • the total number of ⁇ electrons contained in A x and A y is preferably 4 or more and 24 or less, and more preferably 6 or more and 18 or less, from the viewpoint of better expressing the desired effect of the present invention.
  • a combination of A x and A y includes a combination in which A x is an aromatic group having 4 to 30 carbon atoms (carbocyclic aromatic group or heterocyclic aromatic group), and A y is a hydrogen atom, and is preferably one a x and a y are form an unsaturated heterocyclic ring or unsaturated carbon ring together, a x is a group having the following structure,
  • a combination in which A y is a hydrogen atom or an alkyl group which may have a substituent is more preferable, and A x is a group having the following structure,
  • a combination in which A y is a hydrogen atom is particularly preferable.
  • X and Y represent the same meaning as described above.
  • the substituent for the alkyl group which may have a substituent for A y is preferably a cycloalkyl group; a cyano group; a halogen atom such as a fluorine atom;
  • a 1 represents a trivalent aromatic group which may have a substituent.
  • the trivalent aromatic group may be a trivalent carbocyclic aromatic group or a trivalent heterocyclic aromatic group. From the viewpoint of better expressing the desired effect of the present invention, a trivalent carbocyclic aromatic group is preferable, and a trivalent benzene ring group or a trivalent naphthalene ring group represented by the following formula is more preferable.
  • the substituents Y 1 and Y 2 are described for convenience in order to clarify the bonding state (Y 1 and Y 2 represent the same meaning as described above, and the same applies hereinafter). .
  • a 1 groups represented by the following formulas (A11) to (A18) are more preferable, and a group represented by the formula (A11) is particularly preferable.
  • a 1 as a trivalent substituent which may be possessed by the aromatic group, the same ones as exemplified as the substituents of the aromatic groups of the A X and the like.
  • a 1 preferably has no substituent.
  • a 2 and A 3 each independently represents a divalent aromatic group having 4 to 30 carbon atoms which may have a substituent.
  • the aromatic groups of A 2 and A 3 may be monocyclic or polycyclic. Specific examples of A 2 and A 3 include the following.
  • the organic groups mentioned as specific examples of A 2 and A 3 may have a substituent at any position.
  • substituents include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a —C ( ⁇ O) —OR 14 group.
  • R 14 represents an alkyl group having 1 to 6 carbon atoms.
  • the substituent of the organic group A 2, A 3, halogen atom, an alkyl group, an alkoxy group is preferred, the halogen atom is a fluorine atom, the alkyl group, methyl group, ethyl group, propyl group As the alkoxy group, a methoxy group and an ethoxy group are more preferable.
  • Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • the alkyl of 1 to 6 carbon atoms which may have a substituent the same ones as exemplified in the A x and the like.
  • Q 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.
  • polymeric compound (I) can be used individually by 1 type or in combination of 2 or more types.
  • the optical anisotropic body is used. It is preferable to use those exhibiting reverse wavelength dispersion characteristics.
  • the polymerizable compound (I) can be produced, for example, by the reaction shown below.
  • a hydrazine compound (hydrazine compound (3)) represented by formula (3) is converted into a carbonyl compound (carbonyl compound (4)) represented by formula (4) and [hydrazine compound (3): carbonyl compound ( 4)] at a molar ratio of 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1.
  • the polymerizable compound represented by the formula (I) can be produced.
  • the reaction can be carried out by adding an acid catalyst such as an organic acid such as ( ⁇ ) -10-camphorsulfonic acid and paratoluenesulfonic acid; an inorganic acid such as hydrochloric acid and sulfuric acid;
  • an acid catalyst By adding an acid catalyst, the reaction time may be shortened and the yield may be improved.
  • the addition amount of the acid catalyst is usually 0.001 to 1 mol with respect to 1 mol of the carbonyl compound (4). Further, the acid catalyst may be added as it is, or may be added as a solution dissolved in an appropriate solution.
  • the solvent used in this reaction is not particularly limited as long as it is inert to the reaction.
  • alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-pentyl alcohol, amyl alcohol; diethyl ether, Ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane and cyclopentylmethyl ether; ester solvents such as ethyl acetate, propyl acetate and methyl propionate; aromatic hydrocarbons such as benzene, toluene and xylene Solvents; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; amide solvents such as N, N-dimethylformamide,
  • the amount of the solvent used is not particularly limited and can be appropriately determined in consideration of the type of compound used, reaction scale, etc., but is usually 1 to 100 g with respect to 1 g of the hydrazine compound (3).
  • the reaction proceeds smoothly in the temperature range from ⁇ 10 ° C. to the boiling point of the solvent used.
  • the reaction time for each reaction is usually from several minutes to several hours depending on the reaction scale.
  • the hydrazine compound (3) can be produced as follows.
  • a x and A y represent the same meanings as described above.
  • X 1 represents a leaving group such as a halogen atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, etc.
  • the compound represented by the formula (2a) and hydrazine (1) are mixed in a suitable solvent in a molar ratio of (compound (2a): hydrazine (1)) of 1: 1 to 1:20, preferably 1 : 2 to 1:10 to obtain the corresponding hydrazine compound (3a). Further, by reacting the hydrazine compound (3a) with the compound represented by the formula (2b), the hydrazine compound ( 3) can be obtained.
  • hydrazine (1) a monohydrate is usually used.
  • hydrazine (1) a commercially available product can be used as it is.
  • the solvent used in this reaction is not particularly limited as long as it is inert to the reaction.
  • alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-pentyl alcohol, amyl alcohol; diethyl ether, Ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentylmethyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene; n-pentane, n-hexane, n-heptane, etc.
  • Aliphatic hydrocarbon solvents such as: N, N-dimethylformamide, N-methylpyrrolidone, amide solvents such as hexamethylphosphoric triamide; Sulfur-containing solvents such as dimethyl sulfoxide, sulfolane; and two or more of these And the like; a mixed solvent of.
  • alcohol solvents, ether solvents, and mixed solvents of alcohol solvents and ether solvents are preferable.
  • the amount of the solvent to be used is not particularly limited and can be appropriately determined in consideration of the type of compound used, reaction scale, etc., but is usually 1 to 100 g with respect to 1 g of hydrazine.
  • the reaction proceeds smoothly in a temperature range from ⁇ 10 ° C. to the boiling point of the solvent used.
  • the reaction time for each reaction is usually from several minutes to several hours depending on the reaction scale.
  • the hydrazine compound (3) can also be produced by reducing the diazonium salt (5) using a conventionally known method as follows.
  • X ⁇ represents an anion which is a counter ion for diazonium.
  • examples of X ⁇ include inorganic anions such as hexafluorophosphate ion, borofluoride ion, chloride ion, sulfate ion; polyfluoroalkylcarboxylate ion, polyfluoroalkylsulfonate ion, tetraphenylborate ion And organic anions such as aromatic carboxylate ions and aromatic sulfonate ions.
  • a metal salt reducing agent is generally a compound containing a low-valent metal or a compound consisting of a metal ion and a hydride source (“Organic Synthesis Experiment Handbook” 1990, page 810 issued by Maruzen Co., Ltd.) reference).
  • the metal salt reducing agent for example, NaAlH n (OR 15) m , LiAlH 4, iBu 2 AlH, LiBH 4, NaBH 4, SnCl 2, CrCl 2, TiCl 3 , and the like.
  • R 15 represents an alkyl group having 1 to 6 carbon atoms
  • n represents an integer of 1 to 4
  • the diazonium salt (5) can be produced from a compound such as aniline by a conventional method.
  • the carbonyl compound (4) typically has an ether bond (—O—), an ester bond (—C ( ⁇ O) —O—, —O—C ( ⁇ O) —), a carbonate bond (—O—).
  • the ether bond can be formed, for example, as follows.
  • D1-hal hal represents a halogen atom; the same shall apply hereinafter
  • D2-OMet Metal represents an alkali metal (mainly sodium). The same) is mixed and condensed (Williamson synthesis).
  • D1 and D2 represent arbitrary organic groups (the same applies hereinafter).
  • a compound represented by the formula: D1-hal and a compound represented by the formula: D2-OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
  • a compound represented by the formula: D1-J J represents an epoxy group
  • a compound represented by the formula: D2-OH are mixed in the presence of a base such as sodium hydroxide or potassium hydroxide.
  • a base such as sodium hydroxide or potassium hydroxide.
  • a compound represented by the formula: D1-OFN OFN represents a group having an unsaturated bond
  • a compound represented by the formula: D2-OMet are mixed with a base such as sodium hydroxide or potassium hydroxide. In the presence, mixing is carried out for addition reaction.
  • a compound represented by the formula: D1-hal and a compound represented by the formula: D2-OMet are mixed and condensed in the presence of copper or cuprous chloride (Ullman condensation).
  • Formation of an ester bond and an amide bond can be performed as follows, for example.
  • a compound represented by the formula: D1-COOH and a compound represented by the formula: D2-OH or D2-NH 2 are dehydrated in the presence of a dehydration condensing agent (N, N-dicyclohexylcarbodiimide or the like). Allow to condense.
  • a dehydration condensing agent N, N-dicyclohexylcarbodiimide or the like. Allow to condense.
  • a compound represented by the formula: D1-CO-hal is obtained by allowing a halogenating agent to act on the compound represented by the formula: D1-COOH, which is combined with the formula: D2-OH or D2-NH. The compound represented by 2 is reacted in the presence of a base.
  • Y 21 represents Y 21 —C ( ⁇ O) —O— represents Y .Y 1 representing one and becomes group .L of the same meaning as above, a hydroxyl group, a halogen atom, a methanesulfonyloxy group, a leaving group such as a p- toluenesulfonyloxy group.
  • the dihydroxy compound (compound (6)) represented by the formula (6) is reacted with the formula (in the ratio of 1: 2 to 1: 4, preferably 1: 2 to 1: 3).
  • the target compound (4 ′) can be obtained with high selectivity and high yield.
  • the compound (7) is a compound (carboxylic acid) in which L is a hydroxyl group in the formula (7), dehydration condensation of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, etc.
  • the target product can be obtained by reacting in the presence of the agent.
  • the amount of the dehydrating condensing agent to be used is generally 1 to 3 mol per 1 mol of compound (7).
  • the desired product can be obtained by reacting in the presence of a base.
  • a base examples include organic bases such as triethylamine and pyridine; and inorganic bases such as sodium hydroxide, sodium carbonate and sodium hydrogen carbonate.
  • the amount of the base to be used is generally 1 to 3 mol per 1 mol of compound (7).
  • the compound (7) is a compound (mixed acid anhydride) in which L is a methanesulfonyloxy group or p-toluenesulfonyloxy group in the formula (7) is the same as in the case of a halogen atom.
  • solvent used in the above reaction examples include chlorine solvents such as chloroform and methylene chloride; amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and hexamethylphosphoric triamide.
  • Solvents such as 1,4-dioxane, cyclopentylmethyl ether, tetrahydrofuran and tetrahydropyran; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; n-pentane; and aliphatic hydrocarbon solvents such as n-hexane and n-octane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and mixed solvents composed of two or more of these solvents.
  • the amount of the solvent to be used is not particularly limited and can be appropriately determined in consideration of the type of compound used, reaction scale, etc., but is usually 1 to 50 g with respect to 1 g of hydroxy compound (6).
  • Many of the compounds (7) are known compounds, and include an ether bond (—O—), an ester bond (—C ( ⁇ O) —O—, —O—C ( ⁇ O) —), a carbonate bond (—O—).
  • the usual post-treatment operation in organic synthetic chemistry is performed, and if desired, by applying known separation / purification means such as column chromatography, recrystallization method, distillation method, etc.
  • Product can be isolated.
  • the structure of the target compound can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.
  • the polymerizable compound (I) can be produced and obtained by the method described in Japanese Patent Application No. 2011-099525.
  • polymerizable compounds are used together with the polymerizable compound (I).
  • Another polymeric compound can be used individually by 1 type or in combination of 2 or more types.
  • the other polymerizable compound is a polymerizable compound other than the polymerizable compound (I) and is a compound copolymerizable with the polymerizable compound (I).
  • the wavelength dispersion characteristic exhibited by the optical anisotropic body obtained using only the other polymerizable compound (without using the polymerizable compound (I)) is the polymerizable compound ( It is preferable to use a material having a wavelength dispersion characteristic different from that of the optical anisotropic body obtained by using only I).
  • an optical anisotropic body comprising a polymer obtained by polymerization using only the other polymerizable compound as the other polymerizable compound.
  • the optical anisotropic body to be obtained preferably exhibits positive wavelength dispersion or flat wavelength dispersion characteristics.
  • Examples of the other copolymerizable monomer include 4- (2-methacryloyloxyethyloxy) benzoic acid-4′-methoxyphenyl, 4- (6-methacryloyloxyhexyloxy) benzoic acid biphenyl, 4- (2-acryloyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) Benzoic acid-3 ′, 4′-difluorophenyl, 4- (2-methacryloyloxyethyloxy) benzoic acid naphthyl, 4-acryloyloxy-4′-decylbiphenyl, 4-acryloyloxy-4′-cyanobiphenyl, 4- (2-acryloyloxyethyloxy) -4′-cyanobiphenyl, 4- (2- Tacryloyloxy
  • a polymerizable compound capable of obtaining an optical anisotropic body having a flat wavelength dispersion characteristic is preferable from the viewpoint that the wavelength dispersion characteristic can be adjusted more easily.
  • the polymerizable compound exhibiting flat wavelength dispersion characteristics include JP-A 2007-002208, JP-A 2009-173893, JP-A 2009-274984, JP-A 2010-030979, and JP-A 2010-031223.
  • a polymerizable compound (II) represented by the following formula (II), and the like is preferable to use the polymerizable compound (II).
  • Y 11 to Y 16 are each independently a chemical single bond, —O—, —S—, —O—C ( ⁇ O) —, which is the same as Y 1 to Y 6.
  • R 11 represents the same hydrogen atom or alkyl group having 1 to 6 carbon atoms as R 1 .
  • G 11 and G 12 each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent, similar to G 1 and G 2 .
  • the aliphatic group includes —O—, —S—, —O—C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —NR 12.
  • —C ( ⁇ O) —, —C ( ⁇ O) —NR 12 —, —NR 12 —, or —C ( ⁇ O) — may be present.
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms as in R 2 .
  • Z 11 and Z 12 each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, similar to Z 1 and Z 2 .
  • a a represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, as in A x above, and A b is Similar to Ay , at least one fragrance selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon ring and an aromatic heterocycle.
  • An organic group having a ring and having 2 to 30 carbon atoms is represented.
  • the aromatic ring within A a and A b may have a substituent.
  • a a represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • aromatic ring is a cyclic structure having a broad meaning of aromaticity according to the Huckle rule, that is, a cyclic conjugated structure having (4n + 2) ⁇ electrons and a heterostructure such as sulfur and oxygen typified by thiophene and furan. It means that the lone pair of atoms participates in the ⁇ -electron system and exhibits aromaticity.
  • the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of A a may have a plurality of aromatic rings. And having an aromatic hydrocarbon ring and an aromatic heterocycle.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring.
  • aromatic heterocycle examples include 5-membered aromatic heterocycles such as pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring and thiazole ring; pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc. 6-membered aromatic heterocycles; condensed aromatic heterocycles such as benzimidazole ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, carbazole ring; and the like.
  • Aromatic ring within A a may have a substituent at any position.
  • substituents include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and 2 to 6 carbon atoms such as vinyl group and allyl group.
  • An alkenyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; a nitro group; a phenyl group And aryl groups such as naphthyl group; —C ( ⁇ O) —OR group; —SO 2 R group; and the like.
  • R represents the same meaning as described above.
  • the aromatic ring of A a may have a plurality of the same or different substituents, and two adjacent substituents may be bonded together to form a ring.
  • the ring formed may be monocyclic or condensed polycyclic.
  • "the number of carbon atoms" of the organic group having a carbon number of 2 to 30 A a mean, the total number of carbon atoms of the total organic groups that do not contain carbon atoms of substituents (the same in A b to be described later.) .
  • an aromatic hydrocarbon ring group As the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of A a , an aromatic hydrocarbon ring group; an aromatic heterocyclic ring Group: an alkyl group having 3 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group; from an aromatic hydrocarbon ring group and an aromatic heterocyclic group An alkenyl group having 4 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of: a carbon number having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group 4-30 alkynyl groups; and the like.
  • Ab has a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms which may have a substituent of Ab include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl.
  • Examples of the substituent of the alkyl group having 1 to 6 carbon atoms that may have a substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; substituted amino group such as dimethylamino group; methoxy group, ethoxy Group, an alkoxy group having 1 to 6 carbon atoms such as isopropoxy group; nitro group; aryl group such as phenyl group and naphthyl group; —C ( ⁇ O) —OR group; —SO 2 R group; and the like.
  • R represents the same meaning as described above.
  • Examples of the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring for A b are the same as those exemplified for A a above. Is mentioned.
  • a a and A b are shown below. However, in the present invention, A a and A b are not limited to those shown below.
  • [-] represents a bond of an aromatic ring (the same applies hereinafter).
  • a a and A b may be combined to form a ring.
  • an unsaturated heterocyclic ring having 4 to 30 carbon atoms or an unsaturated carbocyclic ring having 6 to 30 carbon atoms which may have a substituent is preferably formed.
  • the unsaturated heterocyclic ring having 4 to 30 carbon atoms and the unsaturated carbocyclic ring having 6 to 30 carbon atoms are not particularly limited and may or may not have aromaticity. Of these, the rings shown below are preferred. In the formula, for convenience, a double bond connecting a ring and a nitrogen atom is shown (the same applies hereinafter).
  • X, Y and Z represent the same meaning as described above.
  • these rings may have a substituent.
  • substituents include a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a —C ( ⁇ O) —OR group, an —SO 2 R group, and the like. It is done.
  • R represents the same meaning as described above.
  • the ring A a and A b are taken together to form, particularly preferred are those shown below.
  • X and Y represent the same meaning as described above, and X and Y are each preferably a sulfur atom and NR 13 (R 13 represents the same meaning as described above).
  • the total number of ⁇ electrons contained in A a and A b are, from the viewpoint of better express the desired effects of the present invention is preferably 4 or more 24 or less.
  • a combination of A a and A b includes a combination in which A x is an aromatic group having 4 to 30 carbon atoms, and A b is a hydrogen atom or an alkyl group which may have a substituent, and A a And A b together form an unsaturated heterocyclic ring or an unsaturated carbocyclic ring, A a is a group having the following structure, and Ab has a hydrogen atom or a substituent.
  • a 11 represents the same trivalent aromatic group that may have a substituent as A 1 .
  • a 12 and A 13 each independently represents a divalent aromatic group having 4 to 30 carbon atoms which may have a substituent, similar to A 2 and A 3 .
  • Q 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, similar to Q 1 .
  • the polymerizable compound (II) can be produced, for example, by the production methods 1 and 2 shown below.
  • a compound represented by the formula (II ′) can be obtained.
  • Step 1 comprises dihydroxy compound (15) and hydrazone compound (13) in a solvent in a molar ratio of (dihydroxy compound (15): hydrazone compound (13)) of 1: 1 to 1: 5, preferably 1: This is a step of obtaining a hydroxy compound (17) by reacting with 1 to 1: 3.
  • the solvent used for the reaction in step 1 is not particularly limited as long as it is inert to the reaction.
  • Examples of the solvent to be used include the same solvents as exemplified in the method for producing the polymerizable compound (I) as being usable in the reaction of the compound (3) and the compound (4).
  • the amount of the solvent to be used is not particularly limited and can be appropriately determined in consideration of the type of compound used, reaction scale, etc., but is usually 1 to 100 g with respect to 1 g of hydrazone compound (13).
  • step 2 the obtained compound (17) is purified or reacted with the compound represented by the formula (18) (compound (18)) without purification, so that the compound (17) is highly selective and has a high yield.
  • step 3 the step of producing the target compound (II ′). This step can be performed in the same manner as the reaction of the compound (6) and the compound (7).
  • the hydrazone compound (13) can be produced as follows.
  • the carbonyl compound represented by the formula (12) and the hydrazine (1) are in a suitable solvent at a molar ratio of (carbonyl compound (12): hydrazine (1)) of 1: 1 to 1:20, preferably Can be reacted at 1: 2 to 1:10 to give the corresponding hydrazone compound (13).
  • the solvent used in this reaction include the same solvents as those exemplified in the reaction between the hydrazine compound (1) and the compound (2a).
  • the compound represented by the formula (17) used in the above method can also be obtained by the method shown below (step 1a).
  • hydrazine is reacted with the dihydroxy compound (15) to obtain a hydrazone compound represented by the formula (19), and this is reacted with a carbonyl compound represented by the formula (20). ) Can be obtained.
  • any reaction after the completion of the reaction, the usual post-treatment operation in organic synthetic chemistry is performed, and if desired, by applying known separation / purification means such as column chromatography, recrystallization method, distillation method, etc. Product can be isolated.
  • separation / purification means such as column chromatography, recrystallization method, distillation method, etc.
  • the structure of the target compound can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.
  • the polymerizable composition used in the present invention contains at least one of the polymerizable compounds (I) and at least one of the other polymerizable compounds.
  • the polymerizable composition used in the present invention those containing at least one of the polymerizable compounds (I) and at least one of the polymerizable compounds (II) are particularly preferable.
  • the polymerizable composition used in the present invention preferably further contains a polymerization initiator from the viewpoint of performing the polymerization reaction of the polymerizable composition more efficiently. What is necessary is just to select and use an appropriate thing as a polymerization initiator used according to the kind of polymeric group which polymeric compound (I) and another polymeric compound have.
  • a radical polymerization initiator is used if the polymerizable group is radically polymerizable
  • an anionic polymerization initiator is used if it is an anionically polymerizable group
  • a cationic polymerization initiator is used if it is a cationically polymerizable group.
  • the radical polymerization initiator either a thermal radical generator or a photo radical generator can be used, but it is preferable to use a photo radical generator.
  • Photo radical generators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds , Xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.
  • a photoradical generator can be used individually by 1 type or in combination of 2 or more types.
  • acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, Examples include 2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone.
  • biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimi
  • a hydrogen donor in combination because sensitivity can be further improved.
  • the “hydrogen donor” means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
  • the hydrogen donor mercaptan compounds, amine compounds and the like defined below are preferable.
  • Examples of mercaptan compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine, etc. Can be mentioned.
  • Examples of amine compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, Examples include 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile.
  • triazine compounds examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri
  • O-acyloxime compounds include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio) phenyl]- Octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl- 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole-3- Yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime), 1-
  • anionic polymerization initiator examples include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene, and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts; and the like.
  • Examples of the cationic polymerization initiator include proton acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride.
  • the blending ratio of the polymerization initiator is 100 parts by weight of the polymerizable compound (the total of the polymerizable compound (I) and the other polymerizable compound is 100 parts by weight, the same shall apply hereinafter), Usually, it is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight.
  • the polymerizable composition used in the present invention further includes other copolymerizable monomers, metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, and gelation described below.
  • Other additives such as agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and metal oxides such as titanium oxide may be blended.
  • the blending ratio of other additives is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable compound.
  • the polymerizable composition used in the present invention is usually appropriately prepared with a predetermined amount of at least one of a predetermined amount of the polymerizable compound (I), a predetermined amount of another polymerizable compound, a polymerization initiator, and other additives as required. It can be prepared by mixing and dissolving in an organic solvent.
  • Organic solvents to be used include ketones such as cyclopentanone, cyclohexanone, and methyl ethyl ketone; acetate esters such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane; 1,4-dioxane, cyclopentylmethyl And ethers such as ether, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane;
  • optical anisotropic body is a molded body made of a polymer obtained by polymerizing the polymerizable composition.
  • polymerization means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.
  • Examples of the shape of the optical anisotropic body according to the present invention include a film shape and a sheet shape.
  • a film-like or sheet-like optically anisotropic substance (A) is obtained by conducting a polymerization reaction of the polymerizable composition in a suitable organic solvent, and then isolating the target polymer and appropriately obtaining the obtained polymer.
  • a solution prepared by diluting with an appropriate organic solvent if desired is applied on a substrate by a known coating method, then desolvated, and then suitably produced by a method of performing a polymerization reaction by heating or irradiating active energy rays. can do.
  • the organic solvent used for the polymerization reaction in the method (A) is not particularly limited as long as it is inert, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene; cyclohexanone, cyclopentanone, methyl ethyl ketone. Ketones such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; ethers such as cyclopentyl methyl ether, tetrahydrofuran and tetrahydropyran; Of these, those having a boiling point of 60 to 250 ° C. are preferred, and those having a temperature of 60 to 150 ° C. are more preferred, from the viewpoint of excellent handleability.
  • examples of the organic solvent for dissolving the polymer include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; And halogenated hydrocarbon solvents such as dichloromethane, chloroform and dichloroethane; ether solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane and cyclopentylmethyl ether;
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone
  • ester solvents such as butyl acetate and amyl acetate
  • halogenated hydrocarbon solvents such as dichloromethane, chlor
  • Examples of the organic solvent used in the method (B) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; dichloromethane, chloroform, dichloroethane, and the like.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone
  • ester solvents such as butyl acetate and amyl acetate
  • dichloromethane chloroform, dichloroethane, and the like.
  • ether solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentylmethyl ether, 1,3-dioxolane;
  • ether solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentylmethyl ether, 1,3-dioxolane;
  • those having a boiling point of 60 to 200 ° C. are preferable from the viewpoint of easy handling.
  • the optical anisotropic body according to the present invention forms an alignment film on a substrate and forms a liquid crystal layer made of a polymer obtained by polymerizing the polymerizable composition on the alignment film. What is obtained is preferable.
  • a substrate to be used a known and usual material can be used regardless of organic or inorganic.
  • organic materials include polycycloolefins (for example, ZEONEX, ZEONOR (registered trademark; manufactured by ZEON CORPORATION), ARTON (registered trademark; manufactured by JSR), and APPEL (registered trademark; manufactured by Mitsui Chemicals)), polyethylene terephthalate.
  • inorganic materials include silicon, glass, calcite, etc. Of these, organic materials are preferred.
  • the substrate used may be a single layer or a laminate. As the substrate, an organic material is preferable, and a resin film using the organic material as a film is more preferable.
  • the alignment film is formed on the surface of the substrate in order to regulate the alignment of the organic semiconductor compound in one direction in the plane.
  • the alignment film contains a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, or polyetherimide.
  • the alignment film can be obtained by applying a solution (composition for alignment film) containing such a polymer on the substrate in the form of a film, drying, and rubbing in one direction.
  • the thickness of the alignment film is preferably 0.001 to 5 ⁇ m, and more preferably 0.001 to 1 ⁇ m.
  • the alignment film or the substrate can be rubbed.
  • the rubbing treatment method is not particularly limited, and examples thereof include a method of rubbing the alignment film in a certain direction with a roll made of a synthetic fiber such as nylon or a natural fiber such as cotton or a felt.
  • a roll made of a synthetic fiber such as nylon or a natural fiber such as cotton or a felt.
  • the alignment film can be provided with a function of regulating the alignment of the cholesteric liquid crystal layer having cholesteric regularity in one direction in a plane by irradiating the surface of the alignment film with polarized ultraviolet rays. it can.
  • known methods can be used, for example, curtain coating.
  • curtain coating Method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method and the like.
  • Examples of the method for polymerizing the polymerizable composition include a method of irradiating active energy rays and a thermal polymerization method, but a method of irradiating active energy rays because the reaction proceeds at room temperature without requiring heating. Is preferred. Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.
  • the temperature during irradiation is preferably 30 ° C. or lower.
  • the ultraviolet irradiation intensity is usually in the range of 1 W / m 2 to 10 kW / m 2 , preferably in the range of 5 W / m 2 to 2 kW / m 2 .
  • the polymer obtained by polymerizing the polymerizable composition can be peeled off from the substrate and used as an optical anisotropic body as it is, or can be used as it is as an organic material for an optical film without being peeled off from the substrate. it can.
  • the adjusting method of the present invention by using a polymerizable composition obtained by controlling and mixing the use ratio of the polymerizable compound (I) and other polymerizable compounds, an arbitrary retardation wavelength dispersion characteristic can be obtained.
  • the optically anisotropic body which it has can be obtained simply.
  • the optical anisotropic body according to the present invention is composed of the polymer of the present invention, it can be manufactured at low cost and can be uniformly polarized in a wide wavelength range, and has excellent performance. It is.
  • the optical anisotropic body according to the present invention include a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, a viewing angle widening plate, a color filter, a low-pass filter, a light polarizing prism, and various optical filters.
  • the reaction solution was poured into 1.5 liters of water and extracted with 500 ml of ethyl acetate.
  • the ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off.
  • Ethyl acetate was distilled off from the filtrate under reduced pressure using a rotary evaporator to obtain a pale yellow solid.
  • the structure of the target product was identified by 1 H-NMR.
  • Step 2 Synthesis of Compound 1>
  • 10.5 g (15.3 mmol) of the intermediate A synthesized in Step 1 above 3.0 g (18.3 mmol) of 2-hydrazinobenzothiazole in a nitrogen stream, And 80 ml of tetrahydrofuran (THF) were added.
  • 18 mg (0.08 mmol) of ( ⁇ ) -10-camphorsulfonic acid was added, and the whole volume was stirred at 25 ° C. for 3 hours.
  • the reaction solution was poured into 800 ml of 10% sodium bicarbonate water and extracted twice with 100 ml of ethyl acetate.
  • Step 2 Synthesis of Compound 2>
  • 3.0 g (4.37 mmol) of Intermediate A synthesized in Step 1 of Compound 1 synthesis in a nitrogen stream 3.0 g (4.37 mmol) of Intermediate A synthesized in Step 1 of Compound 1 synthesis in a nitrogen stream, 1.0 g of Intermediate B synthesized in Step 1 above (5.24 mmol), 30 ml THF, and 15 ml ethanol were added. Further, a solution obtained by dissolving 0.1 g (0.44 mmol) of ( ⁇ ) -10-camphorsulfonic acid in 3 ml of THF was slowly added, and the whole volume was stirred at 25 ° C. for 2 hours.
  • phase difference (Re) between 400 nm and 800 nm of the film having the liquid crystal layer produced in (iii) was measured using an ellipsometer (XLS-100 type, manufactured by JA Woollam). did.
  • the measurement results are shown in the graph of FIG.
  • the vertical axis represents the phase difference (Re (nm)), and the horizontal axis represents the wavelength (nm).
  • ⁇ and ⁇ values were calculated using the following formula. The calculation results are summarized in Table 1 below.
  • the wavelength dispersion characteristics can be changed by changing the ratio of compound 1 and compound 2 used. Specifically, it can be seen that the value of ⁇ gradually increases and the value of ⁇ gradually decreases as the proportion of compound 2 increases. Further, it can be confirmed that the value of ⁇ n gradually increases from the value of Compound 1 alone to the value of Compound 2 alone depending on the ratio. ADVANTAGE OF THE INVENTION According to this invention, the wavelength dispersion of a phase difference can be controlled highly, and the high-quality optical anisotropic body suitable for the objective can be provided.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé d'ajustement de la dispersion des longueurs d'ondes d'un isomère optique, grâce auquel on obtient un isomère optique présentant les caractéristiques recherchées en matière de dispersion des longueurs d'onde en ajustant le rapport de mélange entre un composé polymérisable (I) représenté par la formule (I) et un autre composé polymérisable dans une composition polymérisable lorsque l'isomère optique est produit en utilisant la composition polymérisable contenant le composé polymérisable (I) et l'autre composé. (Dans la formule, chacun des Y1 à Y6 représente -O-C(=O)-, -C(=O)-O- ou équivalent ; chacun des G1 et G2 représente un groupe aliphatique divalent comportant de 1 à 20 atomes de carbone, ou équivalent ; chacun des Z1 et Z2 représente un groupe alcényle comportant de 2 à 10 atomes de carbone, ou équivalent ; Ax représente un groupe organique comportant de 2 à 30 atomes de carbone et au moins un noyau aromatique choisi dans le groupe constitué des noyaux hydrocarbonés aromatiques et des noyaux hétérocycliques aromatiques, ou équivalent ; Ay représente un atome d'hydrogène, un groupe alkyle éventuellement substitué comportant de 1 à 6 atomes de carbone, un groupe organique comportant de 2 à 30 atomes de carbone et au moins un noyau aromatique choisi dans le groupe constitué des noyaux hydrocarbonés aromatiques et des noyaux hétérocycliques aromatiques, ou équivalent ; A1 représente un groupe aromatique trivalent éventuellement substitué ; chacun des A2 et A3 représente un groupe aromatique divalent comportant de 4 à 30 atomes de carbone, ou équivalent ; et Q1 représente un groupe alkyle comportant de 1 à 6 atomes de carbone, ou équivalent.)
PCT/JP2012/067906 2011-07-29 2012-07-13 Procédé d'ajustement de la dispersion des longueurs d'ondes d'un isomère optique et composition polymérisable WO2013018526A1 (fr)

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