JP2009029795A - Polymerizable compound and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new optical film that further controls a wavelength dependence of phase difference value and a new compound that provides the film. <P>SOLUTION: The polymerizable compound is represented by the formula (1) (wherein C1 is a quaternary carbon atom or the like; A1 and A2 are each a cyclic hydrocarbon group or a heterocyclic group; D1 and D2 are each a hydrocarbon group or a heterocyclic group and at least one hydrogen atom contained in D1 and D2 is substituted with an electron withdrawing group; B1 and B2 are each a connecting group or a single bond; X1 and X2 are each a bivalent group represented by the formula (2) (wherein A3 is -C(=O)-C<SB>6</SB>H<SB>4</SB>-, a cyclic hydrocarbon group or a heterocyclic group; B3 is as shown for the B1; and n is an integer of 1-4); E1 and E2 are each an alkylene group; P1 and P2 are each a hydrogen atom or a polymerizable group and at least one of P1 and P2 is a polymerizable group). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a compound suitable for an optical film such as a polarizing plate used in a flat panel display device such as a liquid crystal display device or an organic electroluminescence display device.

Flat panel display devices (hereinafter also referred to as “FPD”) such as liquid crystal display devices (hereinafter also referred to as “LCD”) and organic electroluminescence display devices (hereinafter also referred to as “EL”) are compared with cathode ray tube display devices. Saving space and low power consumption. Therefore, in recent years, FPD has been widely used as a screen of a computer, a television, a mobile phone, a car navigation system, or a portable information terminal. In the FPD, various optical films are generally used for polarizing plates, retardation plates, and the like in order to prevent reflection and expand the viewing angle.
Optical films are required to reduce the wavelength dependence of retardation values. The degree of wavelength dependence of the phase difference value can be expressed by the value of Re (450) / Re (550), and the wavelength dependence of the phase difference value increases as the value becomes larger than 1. means. Here, Re (λ) represents a retardation value of a wavelength λ nm that is transmitted through the optical film.
As a conventional optical film, an optical film obtained by applying a compound represented by the formula (II) onto an alignment film is disclosed in Patent Document 1, and Re (450) / Re ( The value of 550) was 1.065, which was not always sufficient.

JP 2006-58546 A ([Claim 2] [0115])

  There is a need for a novel optical film that can further suppress the wavelength dependence of the retardation value and a novel compound that can provide the film.

（式（１）中、Ｃ１は４級炭素原子又は４級ケイ素原子を表す。
Ａ１及びＡ２は、それぞれ独立に、２価の環状炭化水素基又は２価の複素環基を表す。Ａ１及びＡ２には、アルキル基、アルコキシ基又はハロゲン原子が結合していてもよい。
Ｄ１およびＤ２は、それぞれ独立に、炭化水素基又は複素環基であって、Ｄ１およびＤ２に含まれる少なくとも１つの水素原子は電子吸引基に置換されている基である。Ｄ１およびＤ２は、炭化水素基、アミノ基、エーテル基、チオエーテル基、アミノアルキル基、カルボニル基又は単結合で互いに連結されていてもよい。 Under such circumstances, the present inventors have found a novel optical film capable of suppressing the wavelength dependence of the retardation value and a novel compound capable of providing the film, and have reached the present invention. That is, the present invention
[1] A polymerizable compound represented by the formula (1).

(In Formula (1), C1 represents a quaternary carbon atom or a quaternary silicon atom.
A1 and A2 each independently represent a divalent cyclic hydrocarbon group or a divalent heterocyclic group. An alkyl group, an alkoxy group or a halogen atom may be bonded to A1 and A2.
D1 and D2 are each independently a hydrocarbon group or a heterocyclic group, and at least one hydrogen atom contained in D1 and D2 is a group substituted with an electron-withdrawing group. D1 and D2 may be connected to each other by a hydrocarbon group, an amino group, an ether group, a thioether group, an aminoalkyl group, a carbonyl group, or a single bond.

［式（２）中、Ａ３は、−Ｃ（＝Ｏ）−Ｃ_６Ｈ_４−、２価の環状炭化水素基又は複素環基を表す。該−Ｃ（＝Ｏ）−Ｃ_６Ｈ_４−、２価の環状炭化水素基又は複素環基には、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、トリフルオロメチル基、トリフルオロメチルオキシ基、ニトリル基、ニトロ基又はハロゲン原子が結合していてもよい。Ｂ３は前記Ｂ１と同じ意味を表す。ｎは１〜４の整数を表す。ｎが２〜４の場合には、Ａ３は互いに同一であっても異なっていてもよく、Ｂ３は、互いに同一であっても異なっていてもよい。］ X1 and X2 each independently represent a divalent group represented by the formula (2).

Wherein (2), A3 _{is, -C (= O) -C 6} H 4 -, a divalent cyclic hydrocarbon group or heterocyclic group. The _{-C (= O) -C 6 H} 4 -, 2 divalent cyclic hydrocarbon radicals or heterocyclic group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group , A trifluoromethyloxy group, a nitrile group, a nitro group or a halogen atom may be bonded. B3 represents the same meaning as B1. n represents an integer of 1 to 4. When n is 2 to 4, A3 may be the same as or different from each other, and B3 may be the same as or different from each other. ]

  E1 and E2 each independently represents an alkylene group having 2 to 25 carbon atoms, and E1 and E2 each further represents an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom. Atoms may be bonded.

  P1 and P2 each independently represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group. )

（式（３）及び（４）中、Ｒaは、水素原子、炭素数１〜１８の直鎖状アルキル基、炭素数３〜１８の分岐状アルキル基、炭素数５〜１８のシクロアルキル基、フェニル基、フラニル基又はチオフェニル基を表す。Ｒbは、炭素数１〜１８の直鎖状アルキル基、炭素数３〜１８の分岐状アルキル基、炭素数５〜１８のシクロアルキル基、フェニル基、フラニル基又はチオフェニル基を表す。） [2] The electron withdrawing group bonded to the groups constituting D1 and D2 in the formula (1) is a nitro group, a nitrile group, a trifluoromethyl group, a group represented by the formula (3), and a formula [4] The polymerizable compound as described in [1], which is at least one electron-withdrawing group selected from the group consisting of groups represented by (4).

(In the formulas (3) and (4), Ra is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, Rb represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, a phenyl group, a phenyl group, a furanyl group, or a thiophenyl group. Represents a furanyl group or a thiophenyl group.)

[3] B1 and B2 in the formula (1) are a single bond, —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O). The polymerizable compound according to [1] or [2], which is-or -OC (= O) -O- group.

（式（Ｄ−１）〜（Ｄ−１１）中、ＥＷＧは、それぞれ独立に、電子吸引基を表す。ｐおよびｑはそれぞれ独立に０〜４を表し、ｒは０〜６を表す。但し、上記２価の基が（ＥＷＧ）_ｐおよび（ＥＷＧ）_ｑを有する基である場合、１≦ｐ＋ｑ≦８であり、（ＥＷＧ）_ｒおよび（ＥＷＧ）_ｑを有する化合物の場合、１≦ｒ＋ｑ≦１０である。） [4] Any one of [1] to [3], wherein C1, D1, and D2 are divalent groups selected from the group consisting of formulas (D-1) to (D-11). Polymerizable compound.

(In formulas (D-1) to (D-11), EWG independently represents an electron-withdrawing group. P and q each independently represent 0 to 4, and r represents 0 to 6. In the case where the divalent group is a group having (EWG) _p and (EWG) _q , 1 ≦ p + q ≦ 8, and in the case of a compound having (EWG) _r and (EWG) _q , 1 ≦ r + q ≦ 10)

[5] The polymerizable compound according to any one of [1] to [4], wherein the polymerizable group in formula (1) is an acryloyl group or a methacryloyl group.

［式（１−Ａ）〜（１−Ｃ）中、ｎ１は、それぞれ独立に、１〜３の整数を表し、ｎ２は、それぞれ独立に、２〜１４の整数を表す。Ｒ”は、それぞれ独立に、水素原子またはメチル基を表す。］ [6] The polymerizable compound represented by formula (1) is a compound selected from the group consisting of compounds represented by formulas (1-A) to (1-C) [1] The polymerizable compound according to [5].

[In Formulas (1-A) to (1-C), n1 independently represents an integer of 1 to 3, and n2 independently represents an integer of 2 to 14, respectively. R ″ each independently represents a hydrogen atom or a methyl group.]

[7] A polymerizable compound different from the polymerizable compound according to any one of [1] to [6] and exhibiting liquid crystallinity, and the polymerizable compound according to any one of [1] to [6] The composition characterized by containing.

[8] A polymerizable compound which is different from the polymerizable compound according to any one of [1] to [6] and exhibits liquid crystallinity is represented by formula (I), formula (II), formula (III) or formula The composition according to [7], which is a compound represented by (IV).
P11-B11-E11- (B12-A11) _s -B13-E12-B14-P12 (I)
P11-B11-E11- (A11-B12) _s -E12-B13-P12 (II)
P11-B11-E11- (B12-A11) _s -F11 (III)
P11-B11-E11- (B12-A11) _s -B13-F11 (IV)
[In the formulas (I) to (IV), A11 each independently represents a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group, or a thiophenylene group. A11 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
B11, B12, B13 and B14 are each independently, -CRR '-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O). = N -, - N = N (→ O) -, - C (= O) -NR -, - NR-C (= O) -, - OCH 2 -, - NR -, - CH 2 O -, - SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond (where R and R ′ are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
E11 and E12 each independently represents an alkylene group having 2 to 25 carbon atoms. Further, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom may be bonded to E11 and E12.
P11 and P12 each independently represent a polymerizable group.
F11 represents a hydrogen atom, an alkyl group, a nitrile group, a nitro group, a trifluoromethyl group, or a halogen atom.
s represents the integer of 1-5 each independently. When s is 2 to 5, A11 may be the same as or different from each other, and B12 may be the same as or different from each other. ]

[9] A polymerizable compound different from the polymerizable compound according to any one of [1] to [6] and exhibiting liquid crystallinity, and the polymerizable compound according to any one of [1] to [6] The composition according to [7] or [8], wherein the polymerizable compound according to any one of [1] to [6] is contained in an amount of 3 to 50 parts by weight with respect to 100 parts by weight as a whole.

[10] An optical film comprising a structural unit derived from the polymerizable compound according to any one of [1] to [6].

[11] An optical film obtained by polymerizing the composition according to any one of [7] to [9].

[12] The optical film according to [10] or [11] is a λ / 4 plate showing 113 to 163 nm as a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film. A featured optical film.

[13] The optical film according to [10] or [11] is a λ / 2 plate showing 250 to 300 nm as a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film. A featured optical film.

[14] A polarizing plate comprising the optical film and polarizing film according to any one of [10] to [13].

[15] A flat panel display comprising the polarizing plate and the liquid crystal panel according to [14].

[16] An organic EL display device comprising an organic electroluminescence panel including the polarizing plate according to [14].

[17] A method for producing an unpolymerized film, comprising a step of applying a composition according to any one of [7] to [9] to a supporting substrate and drying the composition.

[18] A method for producing an unpolymerized film, comprising a step of applying and drying the composition according to any one of [7] to [9] on an alignment film formed on a supporting substrate. .

[19] A method for producing an optical film, comprising a step of curing an unpolymerized film obtained by the production method according to [17] or [18] by polymerization.
Etc. are provided.

  According to the present invention, it is possible to obtain an optical film that can further suppress the wavelength dependence of the retardation value and a compound that can provide the film.

The polymerizable compound of the present invention is a polymerizable compound represented by the formula (1) (hereinafter sometimes referred to as “polymerizable compound (1)”).
In formula (1), C1 represents a quaternary carbon atom or a quaternary silicon atom.
Since C1 is a quaternary substituent, the surface formed by A1 and B1 and the surface formed by A2 and B2 are formed at 100 ° to 140 °, preferably 110 ° to 130 °. Accordingly, when the polymerizable compound (1) of the present invention is dissolved in an organic solvent, the compatibility with a liquid crystal compound described later is improved, and the retardation value of the obtained optical film tends to increase. preferable. Among these, quaternary carbon atoms are preferable as C1 because of the ease of production of the polymerizable compound (1).

In formula (1), A1 and A2 each independently represent a divalent cyclic hydrocarbon group having about 5 to 20 carbon atoms or a divalent heterocyclic group having about 5 to 20 carbon atoms.
The divalent cyclic hydrocarbon group used for A1 and A2 includes a cycloalkyl group having about 5 to 12 carbon atoms such as a cyclopentyl group and a cyclohexyl group; an aromatic group having about 6 to 20 carbon atoms represented by the following formula: ,

An alicyclic group composed of a 5-membered ring and a 6-membered ring represented by the following formula,

Examples thereof include a heterocyclic group composed of a 5-membered ring and a 6-membered ring represented by the following formula.

  An alkyl group, an alkoxy group or a halogen atom may be bonded to A1 and A2. For example, a part of hydrogen atoms of the above divalent cyclic hydrocarbon group or divalent heterocyclic group has about 1 to 4 carbon atoms such as methyl group, ethyl group, i-propyl group, t-butyl group, etc. Alkyl group; alkoxy group having about 1 to 4 carbon atoms such as methoxy group and ethoxy group; trifluoromethyl group; trifluoromethyloxy group; nitrile group; nitro group; halogen atom such as fluorine atom, chlorine atom and bromine atom May be substituted.

  Among them, it is preferable that A1 and A2 are the same type of group because production is easy. Moreover, as A1 and A2, a 1,4-phenylene group, a 1,4-cyclohexylene group, and a 3methyl-1,4-phenylene group are preferable because of easy production.

D1 and D2 are each independently a hydrocarbon group or a heterocyclic group, and at least one hydrogen atom contained in D1 and D2 is a group substituted with an electron-withdrawing group.
When either one of D1 and D2 contains an electron withdrawing group, the positive wavelength dispersion is reversed in the reverse direction even if the content of the structural unit derived from the polymerizable compound (1) is small in the obtained optical film. This is preferable because it can be shifted, and the wavelength dispersion characteristics of the resulting optical film tends to be easily controlled. In particular, when both D1 and D2 contain an electron-withdrawing group, a polymerizable compound (1 ) Is preferred because it is easy to synthesize.
The hydrocarbon group contained in D1 and D2 is a cyclic, straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms. Specifically, as a group in which the electron-withdrawing group is not substituted, Examples of the hydrocarbon group include a cycloalkyl group having about 5 to 12 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
Moreover, the aromatic group etc. by which the electron withdrawing group about C6-C20 represented by a following formula is substituted are mentioned.

ここで、ＥＷＧは、それぞれ独立に、電子吸引基を表す。ｐおよびｑはそれぞれ独立に０〜４を表し、ｒは０〜６を表す。但し、上記２価の基が（ＥＷＧ）_ｐおよび（ＥＷＧ）_ｑを有する基である場合、１≦ｐ＋ｑ≦８であり、（ＥＷＧ）_ｒおよび（ＥＷＧ）_ｑを有する化合物の場合、１≦ｒ＋ｑ≦１０である。好ましくは、ｐ＝ｑ＝ｒ＝１である。
通常、電子吸引基は、Ｃ１と結合している炭素原子のβ位の炭素原子に結合している水素原子に置換される。

Here, each EWG independently represents an electron withdrawing group. p and q represent 0-4 each independently, and r represents 0-6. However, when the divalent group is a group having (EWG) _p and (EWG) _q , 1 ≦ p + q ≦ 8, and in the case of a compound having (EWG) _r and (EWG) _q , 1 ≦ r + q ≦ 10. Preferably, p = q = r = 1.
Usually, the electron withdrawing group is substituted with a hydrogen atom bonded to the carbon atom at the β-position of the carbon atom bonded to C1.

式中、ＥＷＧは、それぞれ独立に、電子吸引基を表す。ｔは１〜５の整数を表し、好ましくは、１〜２である。
通常、電子吸引基は、ヘテロ原子のα位の炭素原子に結合している水素原子に置換される。 Examples of the heterocyclic group that can be substituted by the electron-withdrawing group used for D1 and D2 include the following formulas.

In formula, EWG represents an electron withdrawing group each independently. t represents an integer of 1 to 5, and preferably 1 to 2.
Usually, the electron withdrawing group is replaced by a hydrogen atom bonded to the α-position carbon atom of the heteroatom.

Here, examples of the electron withdrawing group include a nitro group, a nitrile group, a trifluoromethyl group, a group represented by the formula (3), a group represented by the formula (4), and the like.
Among these, a nitro group, a nitrile group, and a trifluoromethyl group are preferable because production of the polymerizable compound (1) is easy.

（式（３）及び（４）中、Ｒaは、水素原子、炭素数１〜１８の直鎖状アルキル基、炭素数３〜１８の分岐状アルキル基、炭素数５〜１８のシクロアルキル基、フェニル基、フラニル基又はチオフェニル基を表す。Ｒbは、炭素数１〜１８の直鎖状アルキル基、炭素数３〜１８の分岐状アルキル基、炭素数５〜１８のシクロアルキル基、フェニル基、フラニル基又はチオフェニル基を表す。）

(In the formulas (3) and (4), Ra is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, Rb represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, a phenyl group, a phenyl group, a furanyl group, or a thiophenyl group. Represents a furanyl group or a thiophenyl group.)

  D1 and D2 may be connected to each other by a hydrocarbon group having about 1 to 5 carbon atoms, an amino group, an ether group, a thioether group or a single bond. Here, examples of the hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, and a propylene group, and a linking group in which a single bond of the alkylene group is substituted with a double bond or a triple bond.

式（Ｄ−１）〜（Ｄ−１１）中、ＥＷＧは、それぞれ独立に、電子吸引基を表す。ｐおよびｑはそれぞれ独立に０〜４を表し、ｒは０〜６を表す。但し、ｐおよびｑを有する化合物の場合、１≦ｐ＋ｑ≦８であり、ｒおよびｑを有する化合物の場合、１≦ｒ＋ｑ≦１０である。好ましくは、ｐ＝ｑ＝ｒ＝１である。
また、ＥＷＧは、Ｃ１に対応する炭素原子に対してγ位の炭素原子に結合している水素原子に置換されていることが好ましい。 The divalent group [—C1 (D1D2) —] consisting of C1, D1 and D2 is preferably a substituent in which D1 and D2 are connected to each other. Specific examples include those represented by formulas (D-1) to (D— And a divalent substituent represented by 11).

In formulas (D-1) to (D-11), EWG independently represents an electron withdrawing group. p and q represent 0-4 each independently, and r represents 0-6. However, in the case of a compound having p and q, 1 ≦ p + q ≦ 8, and in the case of a compound having r and q, 1 ≦ r + q ≦ 10. Preferably, p = q = r = 1.
Moreover, it is preferable that EWG is substituted by a hydrogen atom bonded to a carbon atom at the γ position with respect to the carbon atom corresponding to C1.

（式中、ＥＷＧは、−ＮＯ_２、−ＣＮ、−ＣＦ_３などの電子吸引性基を表す。） Among these, (D-1) is preferable from the viewpoint of ease of production, and (D-1-1) represented by the following formula is particularly preferable.

(In the formula, EWG represents an electron-withdrawing group such as —NO ₂ , —CN, and —CF ₃ ).

  In addition, a part of hydrogen atom contained in the structure exemplified above as D1 and D2 is an alkyl group having about 1 to 4 carbon atoms such as methyl group, ethyl group, i-propyl group, t-butyl group; methoxy group An alkoxy group having about 1 to 4 carbon atoms such as ethoxy group; a halogen atom such as fluorine atom, chlorine atom or bromine atom may be substituted.

B1 and B2 are each independently, -CRR '-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -C (= O) -NR-, -NR-C (= O) —, —OCH ₂ —, —NR—, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (= O) —CH═CH— or a single bond. Here, R and R ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group.
B1 and B2 are preferably the same type of divalent group because of easy production.

As B1 and B2, from the viewpoint of ease of production of the polymerizable compound (1), B1 and B2 in the formula (1) are —C (═O) —, —C (═O) —O—. , —O—C (═O) —, —O—C (═O) —O—, —O—, —S—, or a single bond is preferable.
It is preferable that B1 and B2 are the above-described bonding groups because liquid crystallinity is improved and molecular alignment becomes easy.

式（２）中、Ａ３は−Ｃ（＝Ｏ）−Ｃ_６Ｈ_４−、２価の環状炭化水素基、２価の複素環基を表す。具体的にはＡ１及びＡ２で例示された２価の環状炭化水素基及び２価の複素環基が例示され、製造の容易さから、１，４−フェニレン基、１，４−シクロヘキシレン基、３メチル−１，４フェニレン基、３メトキシ−１，４フェニレン基、ベンゼン環の炭素原子が１〜３個窒素原子に置換した２価の基が好ましく、特に、１，４−フェニレン基、１，４−シクロヘキシレン基、３−メチル−１，４フェニレン基、３−メトキシ−１，４フェニレン基が好ましい。 X1 and X2 represent a divalent group represented by the formula (2).

In formula (2), A3 represents —C (═O) —C ₆ H ₄ —, a divalent cyclic hydrocarbon group, and a divalent heterocyclic group. Specifically, the divalent cyclic hydrocarbon group and divalent heterocyclic group exemplified in A1 and A2 are exemplified, and from the ease of production, 1,4-phenylene group, 1,4-cyclohexylene group, A 3-methyl-1,4-phenylene group, a 3-methoxy-1,4-phenylene group, and a divalent group in which 1 to 3 carbon atoms of the benzene ring are substituted with nitrogen atoms are preferable. , 4-cyclohexylene group, 3-methyl-1,4-phenylene group, and 3-methoxy-1,4-phenylene group are preferable.

The —C (═O) —C ₆ H ₄ —, divalent cyclic hydrocarbon group or divalent heterocyclic group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, trifluoro A methyl group, a trifluoromethyloxy group, a nitrile group, a nitro group or a halogen atom may be bonded.
X1 and X2 are preferably the same type of divalent group because of easy production.

B3 represents the same meaning as B1 and B2, and from the standpoint of ease of production, -C (= O)-, -C (= O) -O-, -OC (= O)-, -O- C (═O) —O—, —O—, —S— or a single bond is preferred.
n represents an integer of 1 to 4. When n is 2 or more, A3 may be the same or different from each other, and B3 may be the same or different from each other.
From the viewpoint of easy handling when casting the resulting polymerizable compound, n is preferably 1 or 2, and 1 is particularly preferable because it is easy to produce.

E1 and E2 each independently represent an alkylene group having 2 to 25 carbon atoms, preferably an alkylene group having 4 to 12 carbon atoms.
The hydrogen atom of E1 and E2 may be substituted with an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom, but is preferably not substituted.
It is preferable that E1 and E2 are the same type of alkylene group because production is easy.

［式（Ｐ−１）〜（Ｐ−５）中、Ｒ_１〜Ｒ_５はそれぞれ独立に、炭素数１〜４のアルキル基又は水素原子を表す。］）
で示される基を有する重合性基、式（Ｐ−２）〜（Ｐ−４）で示される基と反応し得る活性水素原子を有する重合性基、活性水素原子を有する重合性基と反応し得る基を有する重合性基などが例示される。
さらに、具体的には、式（Ｐ−１）で表される基を有する基としては、例えば、ビニル基、ｐ−スチルベン基、アクリロイル基、メタクロイル基などが挙げられ、式（Ｐ−２）で表される基を有する基としては、例えば、エポキシ基などが挙げられ、式（Ｐ−２）で表される基を有する基としては、例えば、エポキシ基が挙げられ、式（Ｐ−３）で表される基を有する基としては、例えば、オキセタニル基などが挙げられ、式（Ｐ−２）〜（Ｐ−４）で示される基と反応し得る活性水素原子を有する重合性基としては、例えば、カルボキシル基、水酸基、炭素数１〜４のアルキルアミノ基、アミノ基、アミド基などが挙げられ、活性水素原子を有する重合性基と反応し得る基を有する重合性基としては、例えば、カルボキシル基、メチルカルボニル基、アルデヒド基、イソシアネート基、チオイソシアネート基などが挙げられる。
また、重合性基には、上記例示の基とＥ１及びＥ２を連結するために、Ｂ１及びＢ２として示される基が含まれていてもよい。
中でも、光重合させる際の取扱いが容易な上、製造も容易であることからアクリロイル基又はメタクロイル基が好ましく、とりわけ、アクリロイル基が好ましい。
Ｐ１及びＰ２の少なくとも一方は重合性基であり、好ましくは、Ｐ１及びＰ２はいずれも重合性基であると、得られる光学フィルムの膜硬度が優れる傾向があることから、好ましい。 P1 and P2 each independently represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group.
Here, a polymeric group is a substituent which can superpose | polymerize the polymeric compound of this embodiment, and specifically, P1 and P2 are each independently Formula (P-1)-Formula ( P-5)

[In formulas (P-1) to (P-5), R _{1 to} R ₅ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ])
It reacts with a polymerizable group having a group represented by formula (A), a polymerizable group having an active hydrogen atom that can react with the groups represented by formulas (P-2) to (P-4), and a polymerizable group having an active hydrogen atom. Examples thereof include a polymerizable group having a group to be obtained.
More specifically, examples of the group having a group represented by the formula (P-1) include a vinyl group, a p-stilbene group, an acryloyl group, and a methacryloyl group, and the formula (P-2). Examples of the group having a group represented by formula (I) include an epoxy group, and examples of the group having a group represented by formula (P-2) include an epoxy group, and formula (P-3). Examples of the group having a group represented by) include an oxetanyl group and the like, and a polymerizable group having an active hydrogen atom that can react with the groups represented by the formulas (P-2) to (P-4). Examples include a carboxyl group, a hydroxyl group, an alkylamino group having 1 to 4 carbon atoms, an amino group, an amide group, and the like. As the polymerizable group having a group capable of reacting with a polymerizable group having an active hydrogen atom, For example, carboxyl group, methyl Group, aldehyde group, isocyanate group, and thioisocyanate group.
Moreover, in order to connect E1 and E2 with the said exemplary group, the group shown as B1 and B2 may be contained in the polymeric group.
Among them, an acryloyl group or a methacryloyl group is preferable because the handling at the time of photopolymerization is easy and the production is easy, and an acryloyl group is particularly preferable.
At least one of P1 and P2 is a polymerizable group. Preferably, P1 and P2 are both polymerizable groups because the film hardness of the resulting optical film tends to be excellent.

Specific examples of the polymerizable compound (1) include formulas (1-A), (1-B) and (1-C). Among them, a compound in which n1 in the formula is 2, n2 is 2 to 8, and R ″ is a hydrogen atom is preferable because it is easy to produce and suppresses wavelength dispersion of the obtained optical film.
In the optical film of the present invention, a plurality of different polymerizable compounds (1) may be used as the polymerizable compound (1).

（式（１−Ａ）〜（１−Ｃ）中、ｎ１は、それぞれ独立に、１〜３の整数を表し、ｎ２は、それぞれ独立に、２〜１４の整数を表す。Ｒ”は、それぞれ独立に、水素原子またはメチル基を表す。）

(In formulas (1-A) to (1-C), n1 independently represents an integer of 1 to 3, and n2 independently represents an integer of 2 to 14. R ″ represents each. Independently represents a hydrogen atom or a methyl group.)

Preferable specific examples of the polymerizable compound (1) are polymerizable compounds represented by the formula (1-2) and the formula (1-3).

  As a method for producing the polymerizable compound (1), for example, a carbonyl compound having a structure of C1, D1 and D2, wherein C1 is a carbonyl group, is used, and A1 (A2), B1 ( B2), X1 (X2), E1 (E2), and a method obtained by condensation by allowing a compound containing P1 (P2) to act. Compounds including A1 (A2), B1 (B2), X1 (X2), E1 (E2) and P1 (P2) are A1 (= A2), B1 (= B2), X1 (= X2), E1 (= E2), a compound containing each structural unit of P1 (= P2), condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama It can be produced by bonding by reaction, Buchwald-Hartwig reaction, Wittig reaction, Friedel-Craft reaction, Heck reaction, aldol reaction or the like.

The optical film of the present invention is an optical film containing a structural unit derived from the polymerizable compound (1). Although it may be an optical film containing only a structural unit derived from the polymerizable compound (1), it is a compound different from the polymerizable compound (1) and exhibits liquid crystallinity (hereinafter referred to as a liquid crystal compound). In some cases, the structural unit may be further derived. Including a structural unit derived from a liquid crystal compound is preferred because the orientation increases and the retardation value tends to increase.
At this time, the polymerizable group of P1 and / or P2 contained in the polymerizable compound (1) and the polymerizable group of the liquid crystal compound react with each other so that the polymerizable compound (1) and the liquid crystal compound are copolymerized. Among them, a polymerizable group, particularly an acryloyl group, is preferable because it can be easily photopolymerized.
Moreover, the wavelength dependence of the refractive index of the optical film obtained by changing the content of the structural unit derived from the polymerizable compound (1) contained in the optical film and the content of the structural unit derived from the liquid crystal compound. (Wavelength dispersion) can be controlled.

Specific examples of liquid crystal compounds include: Chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .3 Among compounds described in chiral rod-like liquid crystal molecules, compounds having a polymerizable group may be mentioned. In particular, polymerizable rod-like liquid crystal molecules are preferable. Here, the polymerizable rod-like liquid crystal molecules may be used in combination with a plurality of different liquid crystal compounds as liquid crystal molecules.

Examples of the liquid crystal compound include compounds represented by the following formula (I), formula (II), formula (III), or formula (IV).
P11-B11-E11- (B12-A11) _s -B13-E12-B14-P12 (I)
P11-B11-E11- (A11-B12) _s -E12-B13-P12 (II)
P11-B11-E11- (B12-A11) _s -F11 (III)
P11-B11-E11- (B12-A11) _s -B13-F11 (IV)
[In the formulas (I) to (IV), A11 each independently represents a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group, or a thiophenylene group. A11 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
B11, B12, B13 and B14 are each independently, -CRR '-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O). = N -, - N = N (→ O) -, - C (= O) -NR -, - NR-C (= O) -, - OCH 2 -, - NR -, - CH 2 O -, - SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond (where R and R ′ are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
E11 and E12 each independently represents an alkylene group having 2 to 25 carbon atoms. Further, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom may be bonded to E11 and E12.
P11 and P12 each independently represent a polymerizable group.
F11 represents a hydrogen atom, an alkyl group, a nitrile group, a nitro group, a trifluoromethyl group, or a halogen atom.
s represents the integer of 1-5 each independently. When s is 2 to 5, A11 may be the same as or different from each other, and B12 may be the same as or different from each other. ]

Examples of the liquid crystal compound include compounds represented by the following formulas (I-1) to (I-15),

For example, compounds represented by formula (III-1) to formula (III-6)

などが、入手容易であることから好ましい。 For example, compounds represented by formula (IV-1) to formula (IV-6)

Etc. are preferable because they are easily available.

The wavelength dispersion characteristic of the optical film of the present invention can be arbitrarily determined depending on the content of the structural unit derived from the polymerizable compound (1) in the optical film. When only the liquid crystal compound is used without using the polymerizable compound (1), the resulting optical film is a film exhibiting positive wavelength dispersion. And by increasing the content of the structural unit derived from the polymerizable compound (1) among the structural units in the optical film, the chromatic dispersion can be arbitrarily shifted in the reverse direction from the positive chromatic dispersion.
Specifically, about a composition containing a liquid crystal compound and a polymerizable compound (1), about 2 to 5 types of compositions having different content of structural units derived from the polymerizable compound (1) are prepared, respectively. As will be described later, the retardation value of an optical film obtained by producing an optical film having the same film thickness is obtained, and from the results, the content of the structural unit derived from the polymerizable compound (1) and the optical properties are obtained. The content of structural units derived from the polymerizable compound (1) necessary for obtaining a desired retardation value to the optical film having the above film thickness from the correlation obtained with the retardation value of the film. Can be determined.

As an example of a method for producing an optical film, an optical film containing a structural unit derived from the polymerizable compound (1) of the present invention and a liquid crystal compound will be described below.
First, additives such as a polymerization initiator, a polymerization inhibitor, a photosensitizer, a crosslinking agent, and a leveling agent are added to the polymerizable compound (1), the liquid crystal compound, and the organic solvent as necessary, and the mixed solution is prepared. Prepare. In particular, the organic solvent is preferably contained at the time of film formation because the film formation becomes easy, and the polymerization initiator is preferable because it has a function of curing the obtained optical film.
As a weight ratio of the polymerization compound (1) and the liquid crystal compound in the mixed solution, the polymerization compound (1) is 1 to 50 parts by weight, preferably 1 to 100 parts by weight in total of the polymerization compound (1) and the liquid crystal compound. -30 parts by weight. If it is 1 part by weight or more, the shift from the positive wavelength dispersion to the reverse direction becomes significant, and if it is 50 parts by weight or less, the optical film can be prepared at low cost.

(Polymerization initiator)
In preparing the optical film of the present invention, a polymerization initiator for polymerizing the liquid crystal compound and the polymerizable compound (1) is usually used. A preferred embodiment of the optical film of the present invention includes a method of photopolymerizing a liquid crystal compound or a polymerizable compound (1). Therefore, the polymerization initiator is preferably a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxy ketones, α-amino ketones, iodonium salts, sulfonium salts, and more specifically, Irgacure. 907, Irgacure 819, Irgacure 184, Irgacure 651, Irgacure 250, and Irgacure 369 (all manufactured by Ciba Specialty Chemicals), Seiko All BZ, Seiko All Z, Seiko All BEE (all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka optomer SP-152, Adeka optomer SP-170 (all above, Asahi Denka) and the like can be mentioned.
Moreover, the usage-amount of a polymerization initiator is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and polymeric compound (1), Preferably, 0.5 weight part -10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound.

(Polymerization inhibitor)
In preparing the optical film of the present invention, a polymerization inhibitor may be used. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone and alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl- Examples include radical scavengers such as 1-piperidinyloxy radical, thiophenols, β-naphthylamines, and β-naphthols.
By using the polymerization inhibitor, the polymerization of the liquid crystal compound and the polymerizable compound (1) can be controlled, and the stability of the obtained optical film can be improved. Moreover, the usage-amount of a polymerization inhibitor is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and polymeric compound (1), Preferably, it is 0.5 weight part. -10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound.

[Photosensitizer]
Moreover, you may use a photosensitizer when preparing the optical film of this invention. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone, anthracene having a substituent such as anthracene and alkyl ether, phenothiazine, and rubrene.
By using a photosensitizer, the polymerization of the liquid crystal compound or polymerizable compound (1) can be made highly sensitive. The amount of the photosensitizer used is usually 0.1 to 30 parts by weight, preferably 0.5 parts by weight based on 100 parts by weight of the total of the liquid crystal compound and the polymerizable compound (1). Parts to 10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound.

(Leveling agent)
Furthermore, a leveling agent may be used when preparing the optical film of the present invention. As a leveling agent, for example, an additive for radiation-curing coatings (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), coating additives (by Toray Dow Corning: SH28PA, DC11PA, ST80PA), And paint additives (manufactured by Shin-Etsu Silicone Co., Ltd .: KP321, KP323, X22-161A, KF6001) and the like.
By using a leveling agent, the optical film can be smoothed. Furthermore, in the process of manufacturing the optical film, the fluidity of the mixed solution containing the polymerizable compound (1) is controlled, or the crosslinking density of the optical film obtained by polymerizing the liquid crystal compound or the polymerizable compound (1) is adjusted. can do. Moreover, the specific numerical value of the usage-amount of a leveling agent is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and polymeric compound (1), Preferably, it is 0. .5 to 10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound.

[Organic solvent]
The organic solvent used for the preparation of the mixed solution containing the polymerizable compound (1) and the liquid crystal compound is an organic solvent capable of dissolving the polymerizable compound (1), the liquid crystal compound, and the like. Specifically, methanol, Alcohols such as ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate; acetone, methyl ethyl ketone, cyclo Ketone solvents such as pentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane; toluene, xylene, Aromatic hydrocarbon solvents such as Robenzen, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, ethyl lactate, chloroform and the like. These organic solvents may be used alone or in combination. Among them, the composition of the present invention has excellent compatibility and can be dissolved in alcohol, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, etc. Even if halogenated hydrocarbons such as are not used, they can be dissolved and applied.

The viscosity of the mixed solution containing the polymerizable compound (1) and the liquid crystal compound is usually adjusted to 10 Pa · s or less, preferably about 0.1 to 7 Pa · s so as to be easily applied.
Moreover, the density | concentration of solid content in the said mixed solution is 5-50 weight% normally. When the solid content is 5% or more, the optical film does not become too thin, and the optical anisotropy necessary for optical compensation of the liquid crystal panel tends to be provided. Moreover, since the viscosity of the said mixed solution is low as it is 50% or less, since there exists a tendency for the nonuniformity to arise in the film thickness of an optical film, it is preferable.

Then, the target optical film can be obtained on a support base material by apply | coating a mixed solution to a support base material, drying and polymerizing.
Polymerization is performed by irradiating light such as visible light, ultraviolet light, or laser light if P1 and / or P2 contained in the polymerizable compound (1) and the polymerizable group contained in the liquid crystal compound are photopolymerizable. When cured, if the polymerizable group is thermally polymerizable, it is polymerized by heating.
From the viewpoint of film formability, photopolymerization is preferred, and from the viewpoint of handleability, polymerization by ultraviolet light is particularly preferred.

In the case of photopolymerization, the solvent is preferably dried before the photopolymerization to obtain an unpolymerized film in order to improve the film formability. In the case of thermal polymerization, the polymerization may usually proceed with drying, but the method of obtaining an unpolymerized film by drying most of the solvent before polymerization tends to be excellent in film formability. To preferred.
Examples of the solvent drying method include methods such as natural drying, ventilation drying, and vacuum drying. The specific heating temperature is preferably 10 to 120 ° C, more preferably 25 to 80 ° C. Further, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

  Examples of the application method to the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, a spin coater, etc. are mentioned.

The support substrate may be any material that can form an alignment film on the support substrate. For example, glass, a plastic sheet, a plastic film, and a translucent film can be mentioned. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene, and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, cellulose ester films, polyethylene naphthalates. Examples thereof include a phthalate film, a polycarbonate film, a polysulfone film, a polyethersulfone film, a polyetherketone film, a polyphenylene sulfide film, and a polyphenylene oxide film.
In general, the optical film obtained from the liquid crystal compound and the polymerizable compound (1) is a thin film, and the strength of the film is, for example, a bonding step using the film of the present invention, a step of carrying and storing the film, and the like. Even a necessary process can be easily handled without tearing by using a supporting substrate.

In the film of the present invention, preferably, an alignment film is formed on a support substrate, and a mixed solution is applied. The alignment film has a solvent resistance that does not dissolve by application of a mixed solution containing the polymerizable compound (1), etc., has heat resistance due to solvent removal or heat treatment of liquid crystal alignment, friction due to rubbing, etc. It is necessary for the film to be free from peeling and the like, and is a polymer or a composition containing a polymer.
Examples of the polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and polyoxazole which are hydrolysates thereof. And polymers such as polyethyleneimine, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or may be a mixture of two or more or a copolymer. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  Also, these alignment film materials can be applied after being dissolved in a solvent. The solvent is not particularly limited. Specifically, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, etc .; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma Ester solvents such as butyrolactone and propylene glycol methyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; Toluene , Aromatic hydrocarbon solvents such as xylene, chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimeth Shietan, ethyl lactate, chloroform and the like. These organic solvents may be used alone or in combination.

As the alignment film, a commercially available alignment film may be used as it is. Examples of commercially available alignment films include Saneva (registered trademark, manufactured by Nissan Chemical Co., Ltd.), Optomer (registered trademark, manufactured by JSR), etc., as a modified polyvinyl alcohol. (Registered trademark, manufactured by Kuraray).
If such an alignment film is used, it is not necessary to control the refractive index by stretching, so that in-plane variation in birefringence is reduced. Therefore, there is an effect that it is possible to provide a large optical film that can cope with an increase in the size of the FPD on the support substrate.
As a method for forming an alignment film on the support substrate, for example, the alignment film is formed on the support substrate by applying an alignment film material on the support substrate and then annealing. be able to.
The thickness of the alignment film thus obtained is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, in the optically anisotropic layer formation process mentioned later, a polymeric compound (1), a liquid crystal compound, etc. can be aligned at a desired angle on the said alignment film.
In addition, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. By these, a polymeric compound (1), a liquid crystal compound, etc. can be aligned in a desired direction.
As a method for rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is placed on a stage and brought into contact with the alignment film being conveyed can be used.

[Unpolymerized film preparation process]
If the alignment film is formed on the support substrate, a mixed solution containing the liquid crystal compound and the polymerizable compound (1) is applied onto the alignment film and dried to obtain an unpolymerized film. When this unpolymerized film exhibits a liquid crystal phase such as a nematic phase, it has birefringence due to monodomain alignment. Since this unpolymerized film is oriented at a low temperature of about 0 to 120 ° C., preferably 25 to 80 ° C., a supporting substrate that is not necessarily sufficient with respect to heat resistance as exemplified above can be used as the orientation film. After the orientation, even if it is further cooled to about 30 to 10 ° C., it does not crystallize.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the unpolymerized film preparation step is polymerized and cured. Thereby, the film in which the orientation of the liquid crystal compound and the polymerizable compound (1) is fixed, that is, a polymerized film is obtained. Therefore, it is possible to produce a polymer film having a small change in refractive index in the plane direction of the film and a large change in refractive index in the normal direction of the film.
The method for polymerizing the unpolymerized film is determined according to the types of the liquid crystal compound and the polymerizable compound (1). For example, the unpolymerized film can be polymerized by photopolymerization or thermal polymerization. In the present invention, it is particularly preferable to polymerize an unpolymerized film by photopolymerization. According to this, since an unpolymerized film can be polymerized at a low temperature, the heat resistance selection range of the support base material is expanded. Moreover, it becomes easy to manufacture industrially.
Examples of the method for photopolymerizing the unpolymerized film include a method for polymerizing the unpolymerized film by irradiating the unpolymerized film with ultraviolet rays.
The optical film thus obtained can be produced without using a liquid crystal polymer.

In the unpolymerized film polymerization step, the polymerizable compound (1) and the liquid crystal compound can be crosslinked by photopolymerization. Therefore, there is an effect that it is not easily affected by the change in birefringence due to heat.
Moreover, it is not necessary to use surface treating agents, such as surfactant, for the optical film obtained. That is, since the alignment film used for the optical film of the present invention has good adhesion between the support substrate and the alignment film and adhesion between the alignment film and the optical film, the production of the optical film is easy.
Furthermore, the optical film of the present invention is usually a thin film as compared with a stretched film having an equivalent retardation value.

  In the manufacturing method of the optical film of this invention, the process of peeling a support base material may be included following the said process. By setting it as such a structure, the film obtained becomes a film which consists of an oriented film and an optical film. Moreover, in addition to the process of peeling the said support base material, the process of peeling an alignment film may be further included. By setting it as such a structure, the obtained optical film turns into a film which consists only of an optically anisotropic layer.

The film thickness can be adjusted to give a desired phase difference by appropriately adjusting the amount of the coating solution of the mixed solution and the concentration of the coating solution. In the case of a mixed solution in which the polymerizable compound (1) is constant, the retardation value (retardation value, Re (λ)) of the obtained optical film is determined as shown in Equation (6). In order to obtain (λ), the film thickness d may be adjusted.
Re (λ) = d × Δn (λ) (6)
(In the formula, Re (λ) represents a retardation value at a wavelength λ nm, d represents a film thickness, and Δn (λ) represents a refractive index anisotropy at a wavelength λ nm.)

The optical film thus obtained is excellent in transparency and used as various display films. As described above, the thickness of the layer to be formed varies depending on the retardation value of the obtained film. In the present invention, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.
As described above, in the unpolymerized film preparation step, the unpolymerized film (liquid crystal layer) is laminated on the alignment film laminated on an arbitrary support substrate. Therefore, production cost can be reduced as compared with a method of manufacturing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. Furthermore, it is possible to produce a film using a roll film.
Usually, as a phase difference value, it is about 50-500 nm, Preferably it is 100-300 nm.
By using a film having such optical characteristics, it is possible to optically compensate all FPDs such as liquid crystal panels and organic EL with a thin film.

  In order to use the optical film of the present invention as a broadband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the polymerizable compound (1) is appropriately selected, and according to the formula (6). When the retardation value is a λ / 4 plate, the film thickness is adjusted so that the Re (550) of the obtained optical film is 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In the case of a λ / 2 plate, the film thickness should be adjusted so that the Re (550) of the obtained optical film is 250 to 300 nm, preferably 273 to 277 nm, particularly preferably about 275 nm. That's fine.

  In order to use the optical film of the present invention as an optical film for a VA (vertical alignment) mode, by appropriately selecting the content of the structural unit derived from the polymerizable compound (1), according to the formula (6), What is necessary is just to adjust a film thickness so that the phase difference value of the optical film obtained may become Re (550), Preferably it is 40-100 nm, More preferably, it is about 60-80 nm.

The optical film of the present invention can be widely used as an optical film having excellent wavelength dispersion characteristics. Examples of the optical film include an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, and an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. be able to. Moreover, although the optical film of the invention shows excellent optical properties even with one sheet, a plurality of sheets may be laminated.
Moreover, you may combine with another film. Specifically, an elliptical polarizing plate in which the optical film of the present invention is bonded to a polarizing film, a broadband circular polarizing plate in which the optical film of the present invention is further bonded as a broadband λ / 4 plate to the elliptical polarizing plate, and the like. Can be mentioned.
Furthermore, the film concerning this invention can be utilized also for the flat panel display apparatus provided with the phase difference plate of a reflection type liquid crystal display and an organic electroluminescent (EL) display, and the said phase difference plate and the said optical film. The flat panel display device is not particularly limited, and examples thereof include a liquid crystal display device (LCD) and organic electroluminescence (EL).

Thus, the film according to the present invention can be used in a wide range of applications. For example, among these, a polarizing plate formed by laminating an optical film and a polarizing film according to the present invention and a flat panel display device including the polarizing plate will be described below. The polarizing plate according to the present invention has a polarizing function. It is obtained by laminating the optical film directly on one or both sides of a film, that is, a polarizing film, or using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 1 and 2, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.
For example, as shown in FIGS. 1 (a) to 1 (e), (1) an embodiment in which an optical film 1 and a polarizing film layer 2 are directly bonded (FIG. 1 (a)), (2) Embodiment (FIG. 1B) in which the optical film 1 and the polarizing film layer 2 are bonded via the adhesive layer 3, (3) directly bonding the optical film 1 and the optical film 1 ′, Embodiment (FIG. 1 (c)) in which optical film 1 ′ and polarizing film layer 2 are directly bonded, (4) optical film 1 and optical film 1 ′ are bonded through adhesive layer 3, Embodiment (FIG. 1 (d)) in which the polarizing film layer 2 is directly bonded onto the optical film 1 ′, and (5) the optical film 1 and the optical film 1 ′ are bonded through the adhesive layer 3, The optical film 1 ′ and the polarizing film layer 2 are connected via the adhesive layer 3 ′. A bonded embodiment (FIG. 1 (e)) is exemplified.

As a polarizing plate of this invention, a polarizing film and the optical film of this invention are bonded together. The optical film (hereinafter sometimes referred to as a liquid crystal layer) may be a film containing only a structural unit derived from the polymerizable compound (1), or a laminate comprising a support substrate, an alignment film and a liquid crystal layer. A film, and a laminated film composed of an alignment film and a liquid crystal layer can also be used.
The polarizing plate of the present invention may be formed by laminating a plurality of optical films, and the plurality of optical films may be the same or may be used in combination. When it demonstrates more concretely, as a polarizing plate concerning this invention, the structure shown to Fig.2 (a)-(k) is illustrated.
2A to 2E, the optical film 1 and the optical film 1 ′ include a liquid crystal layer 11 or a liquid crystal layer 11 ′ (optical anisotropic layer) and an alignment film layer 12 or an alignment film layer 12 ′. A film is used. 2A to 2E show a configuration in which the optical film 1 and the polarizing film layer 2 are directly bonded to each other (FIG. 2A), and the optical film 1 and the polarizing film layer 2 are the adhesive layer 3 respectively. (FIG. 2 (b)), optical film 1 and optical film 1 ′ are directly bonded, and optical film 1 ′ and polarizing film layer 2 are directly bonded (FIG. 2 (2)). c)), the optical film 1 and the optical film 1 ′ are bonded together via the adhesive layer 3, and the polarizing film layer 2 is bonded directly on the optical film 1 ′ (FIG. 2 (d)), The optical film 1 and the optical film 1 ′ are bonded through the adhesive layer 3, and the optical film 1 ′ and the polarizing film layer 2 are bonded through the adhesive layer 3 ′ (FIG. 2 ( e)).

2 (f) and 2 (g), the optical film 1 and the optical film 1 ′ use a liquid crystal layer 11 or a film made of the liquid crystal layer 11 ′. The optical film 1 has an alignment film layer 12. Alternatively, the alignment film layer 12 ′ is not included. In FIG. 2 (f), the optical film 1 and the polarizing film layer 2 are bonded together via a pair of adhesive layers 3. On the other hand, in FIG.2 (g), the optical film 1 and optical film 1 'are bonded together through the adhesive layer 3, and also the polarizing film layer 2 is bonded outside through the adhesive layer 3'. ing.
FIG. 2 (h) shows the same structure as FIG. 2 (f). However, unlike FIG.2 (f), as the film 1, the support base material 13, the alignment film 12 formed on the surface of the support base material 13, and the liquid crystal layer formed on the surface of the alignment film 12 11 is used.
FIG. 2 (i) shows the same structure as FIG. 2 (g). However, unlike FIG. 2 (g), the optical film 1 and the optical film 1 ′ are formed on the surface of the supporting base material 13 or the supporting base material 13 ′ and the supporting base material 13 or the supporting base material 13 ′. A laminate (film) including the alignment film 12 or the alignment film 12 ′ and the liquid crystal layer 11 or the liquid crystal film 11 ′ formed on the surface of the alignment film 12 or the alignment film 12 ′ is used.
2 (j) and (k) show the same structure as FIG. 2 (g). However, of the two films, in FIG. 1 (j), a film made of the liquid crystal layer 11 ′ is used as the optical film 1 ′, and a film made of the liquid crystal layer 11, the alignment film 12, and the support substrate 13 as the optical film 1. Is used. In FIG. 2 (k), a film composed of the liquid crystal layer 11 ′, the alignment film 12 and the support substrate 13 is used as the optical film 1 ′, and a film composed of the liquid crystal layer 11 is used as the optical film 1.

The polarizing film layer may be a film having a polarizing function, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film, or a film obtained by stretching a polyvinyl alcohol film, or an iodine or dichroic dye. The film etc. which adsorb | sucked are mentioned.
The adhesive used for the adhesive layer 3 and the adhesive layer 3 ′ is preferably an adhesive having high transparency and excellent heat resistance. As such an adhesive, for example, an acrylic, epoxy, or urethane adhesive is used.
Moreover, in a polarizing film, as shown in FIG.1 (c)-FIG.1 (e), as for an optical film, you may laminate | stack 1 layer-3 layers as needed.

The flat panel display device of the present invention includes the optical film of the present invention. For example, a liquid crystal display device including a liquid crystal panel in which the polarizing film of the present invention and a liquid crystal panel are bonded together, or the polarizing film of the present invention. And an organic EL display device including an organic electroluminescence (hereinafter also referred to as “EL”) panel in which a light emitting layer is bonded.
As embodiments of a flat panel display device according to the present invention, a liquid crystal display device and an organic EL display device will be described in detail below.

[Liquid Crystal Display]
Examples of the liquid crystal display device include a liquid crystal display device including a liquid crystal panel as shown in FIG. The liquid crystal panel is formed by bonding the polarizing plate 4 of the present invention and the liquid crystal panel 6 through an adhesive layer 5. According to the above configuration, when a voltage is applied to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules are driven to produce an optical shutter effect.

[Organic EL display device]
Examples of the organic EL display device include an organic EL display device including the organic EL panel shown in FIG. The organic EL panel is formed by laminating the polarizing film 4 of the present invention and the light emitting layer 7 through the adhesive layer 5.
In the organic EL panel, the polarizing film 4 functions as a broadband circularly polarizing plate. The light emitting layer 7 is at least one layer made of a conductive organic compound.

The optical film of the present invention is an optical film that exhibits wavelength dispersion characteristics (reverse wavelength dispersion characteristics) obtained by shifting positive wavelength dispersion in the reverse direction, and is derived from the polymerizable compound (1) that is a structural unit that provides such characteristics. Since the content of the structural unit is small, it can be provided at low cost.
Moreover, it can have a desired phase difference in a wide band. Thus, the optical film can be used as a λ / 4 plate or a λ / 2 plate even with a single optical film.
Furthermore, when the polymerizable compound (1) of the present invention is used as a monomer for a polymer for an optical film, it is excellent in compatibility and can be dissolved in a general-purpose organic solvent. By adding a small amount of the polymerizable compound (1), it can be shifted in the direction opposite to the positive wavelength dispersion.

  The polymerizable compound of the present invention is a simple method for producing an optical film having excellent wavelength dispersion characteristics, such as an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, and a viewing angle widening film. Give in. The optical film of the present invention can be used for flat panel display devices (FPD) such as liquid crystal display devices (LCD) and organic electroluminescence (EL).

Hereinafter, the present invention will be described in more detail with reference to examples.
<Production Example of Polymerizable Compound (1-1)>
The polymerizable compound (1-1) has the following structure. The synthesis example is shown below.

(Synthesis example of ethyl 4- (6-hydroxyhexyloxy) benzoate (PG-a))
150 g (0.90 mol) of ethyl 4-hydroxybenzoate, 186 g (1.35 mol) of potassium carbonate and 750 g of N, N-dimethylacetamide were added, and the temperature was raised to 80 ° C. Subsequently, 244 g (1.24 mol) of 6-bromohexanol was added dropwise over 2 hours, and then stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was poured into ice water and extracted with ethyl acetate. After washing the ethyl acetate phase with water, the solvent was distilled off under reduced pressure to obtain 312 g of a white solid mainly composed of ethyl 4- (6-hydroxyhexyloxy) benzoate (PG-a).

(Synthesis example of 4- (6-hydroxyhexyloxy) benzoic acid (PG-b))
312 g of a white solid mainly composed of (PG-a) obtained in the previous section was dissolved in methanol. Subsequently, a methanol solution containing potassium hydroxide in a saturated state (328 g (5.85 mol) of potassium hydroxide) was added dropwise and stirred at about 70 ° C. for 8 hours. After cooling, 600 g of 36% hydrochloric acid was slowly added. The precipitated white solid was filtered off while washing with water, and dried under reduced pressure at 50 ° C. to give 195 g (0.82 mol) of a white solid mainly composed of 4- (6-hydroxyhexyloxy) benzoic acid (PG-b). Got. The yield was 91% based on (PG-a).

(Synthesis example of 4- (6-acryloxyhexyloxy) benzoic acid (PG-c))
The inside of a container containing 195 g (0.82 mol as (PG-b)) and N, N-dimethylaniline containing (PG-b) as a main component obtained in the previous section and 208 g of N, N-dimethylaniline was replaced with nitrogen. Dissolved with 4-dioxane. The reaction solution was heated to 70 ° C., 148 g (1.64 mol) of acrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, the ethyl acetate phase was washed with water, and the solvent was evaporated under reduced pressure to give 4- (6-acryloylhexyloxy) benzoic acid (PG-c ) 120 g (0.41 mol) of a white solid whose main component was obtained. The yield was 50% based on (PG-b).

(Synthesis example of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d))
166 g (1.2 mol) of 4-hydroxybenzoic acid, 121 g (1.2 mol) of triethylamine and 1193 g of chloroform were placed in a container and stirred. At room temperature, a mixed solution of 113 g (1.2 mol) of chloromethyl ethyl ether and 298 g of chloroform was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours. After cooling, the reaction solution was separated and washed in the order of water, aqueous hydrochloric acid solution and aqueous sodium carbonate solution, and the organic layer was taken out. The organic layer was distilled off under reduced pressure to obtain 251 g of yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d).

(Synthesis example of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e))
To 124 g of a yellow liquid mainly composed of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d) obtained in the previous item, 147 g (0.50 mol) of white solid (PG-c) obtained in the previous item, 4- Dimethylaminopyridine (7.7 g, 63 mmol) and chloroform (824 g) were added. Subsequently, 123 g (0.60 mol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 165 g of chloroform, added dropwise at room temperature, and stirred for 24 hours. Then, the organic layer obtained by filtering to remove the solid was separated and washed twice with 989 g of 2N hydrochloric acid. The solvent was distilled off from the washed organic layer to obtain 237 g of a pale yellow liquid. 474 g of ethanol and 12.7 g (50 mmol) of paratoluenesulfonic acid pyridinium salt were added to the obtained liquid, and the mixture was stirred at 60 ° C. for 3 hours. When the reaction solution was cooled to room temperature, white crystals were precipitated, and thus filtered to take out a solid. The obtained solid was carefully washed with ethanol and dried to obtain 180 g of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e). The yield was 86% based on (PG-c).

  In a container, 4.6 g (13 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, 10.7 g (32 mmol) of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e) ), 0.3 g (3 mmol) of 4-dimethylaminopyridine and 107 g of chloroform, and then 5.4 g (26 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 21 g of chloroform and added dropwise at room temperature. Stir for 24 hours. Then, after adding 107 g of 2N hydrochloric acid, the solid substance was removed by filtration, the filtrate was separated, and the organic layer was taken out. After adding 107 g of 2N hydrochloric acid to the obtained organic layer and separating and washing, the solvent was distilled off and added to methanol to obtain a solid. The obtained solid was carefully washed with methanol. 8.6 g of polymerizable compound (1-1) which was a pale yellow solid was obtained. The yield was 58% based on 9,9-bis (4-hydroxyphenyl) fluorene.

⁽¹ H NMR data of polymerizable compound (1-1))
¹ H NMR (CDCl ₃ ); δ 1.46-1.88 (m, 16H), 4.06 (t, 4H), 4.18 (t, 4H), 5.79-5.85 (m, 2H), 6.07-6.18 (m, 2H), 6.37-6.45 (m, 2H), 6.96-7.00 (m, 4H), 7.08-7.12 ( m, 4H), 7.26-7.45 (m, 14H), 7.77-7.81 (m, 2H), 8.13-8.16 (m, 4H), 8.22-8. 26 (m, 4H)

<Production Example of Polymerizable Compound (1-2)>
The polymerizable compound (1-2) has the following structure. The synthesis example is shown below.

(Synthesis example of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene)
In a container, 25.0 g (93 mmol) of 2,7-dinitro-9-fluorenone, 87 g (925 mmol) of phenol, 0.49 g (5 mmol) of 3-mercaptopropionic acid, and 4.5 g of sulfuric acid were mixed. Stir for hours. When the reaction solution was added to a container containing 35 g of methanol and 70 g of water, crystals were precipitated. The crystals were separated by filtration to yield 24.1 g (55 mmol) of 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene as yellow crystals, and the yield was 2,7-dinitro-9-fluorenone standard. 59%.

  Except for using 9,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene obtained in the previous section instead of 9,9-bis (4-hydroxyphenyl) fluorene, <polymerizable compound (1 In the same manner as in Production Example 1), 11.7 g of a polymerizable compound (1-2) as a pale yellow solid was obtained. The yield was 64% based on 2,7-dinitro-9,9-bis (4-hydroxyphenyl) fluorene.

⁽¹ H NMR data of polymerizable compound (1-2))
¹ H NMR (CDCl ₃ ); δ 1.46-1.88 (m, 16H), 4.07 (t, 4H), 4.19 (t, 4H), 5.80-5.85 (m, 2H), 6.07-6.18 (m, 2H), 6.37-6.45 (m, 2H), 6.96-7.01 (m, 4H), 7.13-7.38 ( m, 12H), 8.01 to 8.05 (m, 2H), 8.13 to 8.42 (m, 12H)

<Production Example of Polymerizable Compound (1-3)>
The polymerizable compound (1-3) has the following structure. The synthesis example is shown below.

(Synthesis example of 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene)
A container containing 25.0 g (73 mmol) of 2,7-dibromo-9-fluorenone, 76 g (732 mmol) of phenol, 0.7 g (7 mmol) of 3-mercaptopropionic acid, and 3.4 g of sulfuric acid was heated to 90 ° C. Aged for 3 hours. When the reaction solution was added to a container containing 78 ml of methanol and 306 g of water, crystals were precipitated. The crystals were separated by filtration and washed with toluene to obtain 31.1 g of 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene as white crystals. The yield was 84% based on 2,7-dibromo-9-fluorenone.

(Synthesis example of 2,7-dicyano-9,9-bis (4-hydroxyphenyl) fluorene)
2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene (33.1 g, 63 mmol), copper cyanide (14.2 g, 142 mmol), and N, N-dimethylformamide (171 ml) were mixed in a container at 153 ° C. For 6 hours. The reaction solution was added to a container containing 171 ml of ethylenediamine and 1709 g of water, and extracted twice with 1282 ml of ethyl acetate to obtain an ethyl acetate phase. After the obtained ethyl acetate phase was washed with water, the solvent was distilled off and recrystallization was performed with ethanol to obtain crystals. The obtained crystals were purified by column chromatography to obtain 6.2 g of 2,7-dicyano-9,9-bis (4-hydroxyphenyl) fluorene as pale yellow crystals. The yield was 24% based on 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene.

  Except for using 9,7-dicyano-9,9-bis (4-hydroxyphenyl) fluorene obtained in the previous section in place of 9,9-bis (4-hydroxyphenyl) fluorene, <polymerizable compound (1 In the same manner as in Production Example 1), 7.9 g of a polymerizable compound (1-3) as a pale yellow solid was obtained. The yield was 83% based on 2,7-dicyano-9,9-bis (4-hydroxyphenyl) fluorene.

⁽¹ H NMR data of polymerizable compound (1-3))
¹ H NMR (CDCl ₃ ); δ 1.46 to 1.91 (m, 16H), 4.07 (t, 4H), 4.19 (t, 4H), 5.80 to 5.85 (m, 2H), 6.07-6.18 (m, 2H), 6.37-6.45 (m, 2H), 6.96-7.00 (d, 4H), 7.16-7.36 ( m, 8H), 7.37-7.41 (m, 4H), 7.71-7.78 (m, 4H), 7.92-7.95 (m, 2H), 8.13-8. 17 (m, 4H), 8.23 to 8.29 (m, 4H)

Example 1
<Example of optical film production>
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after heating and drying, a 89 nm thick film was obtained. Subsequently, the surface was subjected to rubbing treatment, and then a coating solution (mixed solution) having the composition shown in Table 1 was applied to the surface subjected to rubbing treatment by a spin coating method and dried at 45 ° C. for 1 minute. Subsequently, after leaving at room temperature for 1 minute, an ultraviolet ray of 1200 mJ / cm ² was irradiated to produce an optical film having a thickness of 0.98 μm.
In Table 1, LC242 is a liquid crystal compound obtained from BASF, the photopolymerization initiator is Irgacure 907 (manufactured by Ciba Specialty Chemicals), the leveling agent is BYK361N (manufactured by Big Chemie Japan), and the solvent is cyclo Pentanone was used. Moreover, the weight% in the tables other than the solvent means the weight% of the solid content with the coating solution being 100% by weight.

<Measurement of wavelength dispersion characteristics>
In the wavelength range of 450 nm to 700 nm, the retardation value of the created optical film is measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments), and the retardation value Re (450) at a wavelength of 450 nm is measured with the program attached to the apparatus. When the phase difference value Re (550) at the wavelength of 550 nm and the phase difference value Re (650) at the wavelength of 650 nm were calculated, [Re (450) / Re (550)] = 1.059, [Re (650) / Re (550)] was found to be 0.966. The results are shown in Table 2.

(Example 2)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used, and an optical film having a thickness of 1.00 μm was prepared. About the obtained optical film, when the phase difference value was measured using the measuring device (KOBRA-WR, Oji Scientific Instruments company), [Re (450) / Re (550)] = 1.063, [Re ( 650) / Re (550)] was found to be 0.964. The results are shown in Table 2.

(Comparative Example 1)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used, and an optical film having a thickness of 1.09 μm was prepared. About the obtained optical film, when the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make), [Re (450) / Re (550)] = 1.070, [Re ( 650) / Re (550)] was found to be 0.960. The results are shown in Table 2.

(Comparative Example 2)
An optical film was produced in the same manner as in Example 1 except that the coating liquid shown in Table 1 was used, and an optical film having a thickness of 1.04 μm was prepared. About the obtained optical film, when the retardation value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company), [Re (450) / Re (550)] = 1.068, [Re ( 650) / Re (550)] was found to be 0.960. The results are shown in Table 2.

  The value of [Re (450) / Re (550)] in the optical film described in the examples is the optical film described in the comparative example and the optical film composed of the compound represented by the formula (II) shown in Patent Document 1. It can be seen that the wavelength dependency of the phase difference value is small. When the value of ([Re (450) / Re (550)] − [Re (650) / Re (550)]) is examined, the value of the example is less than 0.1. The optical film composed of the compound represented by the formula (II) shown in the comparative example and Patent Document 1 exceeds 0.1, and it can be seen that the wavelength dependence of the retardation value is small in a wide wavelength region.

  According to the present invention, it is possible to obtain an optical film that can further suppress the wavelength dependence of the retardation value and a compound that can provide the film.

It is sectional drawing of an example of the polarizing plate which concerns on this invention. It is sectional drawing of an example of the polarizing plate which concerns on this invention. It is sectional drawing of an example of the liquid crystal panel which concerns on this invention. It is sectional drawing of an example of the organic electroluminescent panel which concerns on this invention.

Explanation of symbols

1, 1 ′ optical film 2, 2 ′ polarizing film layer 3, 3 ′, 3 ″ adhesive layer 4 polarizing plate 5 adhesive layer 6 liquid crystal panel 7 light emitting layer 11, 11 ′ liquid crystal layer (polymerizable compound (1) Containing structural units derived from
Layer consisting only of film)
12, 12 ′ Alignment film layer 13, 13 ′ Support base material

Claims (19)

A polymerizable compound represented by the formula (1):

(In Formula (1), C1 represents a quaternary carbon atom or a quaternary silicon atom.
A1 and A2 each independently represent a divalent cyclic hydrocarbon group or a divalent heterocyclic group. An alkyl group, an alkoxy group or a halogen atom may be bonded to A1 and A2.
D1 and D2 are each independently a hydrocarbon group or a heterocyclic group, and at least one hydrogen atom contained in D1 and D2 is a group substituted with an electron-withdrawing group. D1 and D2 may be connected to each other by a hydrocarbon group, an amino group, an ether group, a thioether group, an aminoalkyl group, a carbonyl group, or a single bond.
B1 and B2 are each independently, -CRR '-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= S)-, -C (= S) -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -C (= O) -NR-, -NR-C (= O) —, —OCH ₂ —, —NR—, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (= O) —CH═CH— or a single bond. Here, R and R ′ each independently represents a hydrogen atom or an alkyl group.
X1 and X2 each independently represent a divalent group represented by the formula (2).

Wherein (2), A3 _{is, -C (= O) -C 6} H 4 -, a divalent cyclic hydrocarbon group or heterocyclic group. The _{-C (= O) -C 6 H} 4 -, 2 divalent cyclic hydrocarbon radicals or heterocyclic group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group , A trifluoromethyloxy group, a nitrile group, a nitro group or a halogen atom may be bonded. B3 represents the same meaning as B1. n represents an integer of 1 to 4. When n is 2 to 4, the structural units composed of A3 and B3 may be the same as or different from each other. ]
E1 and E2 each independently represents an alkylene group having 2 to 25 carbon atoms, and E1 and E2 each further represents an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom. Atoms may be bonded.
P1 and P2 each independently represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group. ) The electron withdrawing group bonded to the groups constituting D1 and D2 in the formula (1) is a nitro group, a nitrile group, a trifluoromethyl group, a group represented by the formula (3), and the formula (4). The polymerizable compound according to claim 1, wherein the polymerizable compound is at least one electron-withdrawing group selected from the group consisting of

(In the formulas (3) and (4), Ra is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, Rb represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, a phenyl group, a phenyl group, a furanyl group, or a thiophenyl group. Represents a furanyl group or a thiophenyl group.)   B1 and B2 in formula (1) are a single bond, —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, or The polymerizable compound according to claim 1, wherein the polymerizable compound is a —O—C (═O) —O— group. The polymerizable compound according to claim 1, wherein C1, D1, and D2 are divalent groups selected from the group consisting of formulas (D-1) to (D-11).

(In formulas (D-1) to (D-11), EWG independently represents an electron-withdrawing group. P and q each independently represent 0 to 4, and r represents 0 to 6. In the case where the divalent group is a group having (EWG) _p and (EWG) _q , 1 ≦ p + q ≦ 8, and in the case of a compound having (EWG) _r and (EWG) _q , 1 ≦ r + q ≦ 10)   The polymerizable compound according to claim 1, wherein the polymerizable group in formula (1) is an acryloyl group or a methacryloyl group. The polymerizable compound represented by the formula (1) is a compound selected from the group consisting of compounds represented by the formulas (1-A) to (1-C). Polymerizable compound.

[In Formulas (1-A) to (1-C), n1 independently represents an integer of 1 to 3, and n2 independently represents an integer of 2 to 14, respectively. R ″ each independently represents a hydrogen atom or a methyl group.]   A polymerizable compound different from the polymerizable compound according to any one of claims 1 to 6 and having a liquid crystallinity, and the polymerizable compound according to any one of claims 1 to 6, Composition. A polymerizable compound that is different from the polymerizable compound according to any one of claims 1 to 6 and exhibits liquid crystallinity is represented by the formula (I), the formula (II), the formula (III), or the formula (IV). The composition according to claim 7, which is a compound to be obtained.
P11-B11-E11- (B12-A11) _s -B13-E12-B14-P12 (I)
P11-B11-E11- (A11-B12) _s -E12-B13-P12 (II)
P11-B11-E11- (B12-A11) _s -F11 (III)
P11-B11-E11- (B12-A11) _s -B13-F11 (IV)
[In the formulas (I) to (IV), A11 each independently represents a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group, or a thiophenylene group. A11 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
B11, B12, B13 and B14 are each independently, -CRR '-, - C≡C - , - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -OC (= S) -O-, -CH = N-, -N = CH-, -N = N-, -N (→ O). = N -, - N = N (→ O) -, - C (= O) -NR -, - NR-C (= O) -, - OCH 2 -, - NR -, - CH 2 O -, - SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond (where R and R ′ are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
E11 and E12 each independently represents an alkylene group having 2 to 25 carbon atoms. Further, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom may be bonded to E11 and E12.
P11 and P12 each independently represent a polymerizable group.
F11 represents a hydrogen atom, an alkyl group, a nitrile group, a nitro group, a trifluoromethyl group, or a halogen atom.
s represents the integer of 1-5 each independently. When s is 2 to 5, A11 may be the same as or different from each other, and B12 may be the same as or different from each other. ]   A total of 100 parts by weight of the polymerizable compound different from the polymerizable compound according to any one of claims 1 to 6 and exhibiting liquid crystallinity, and the polymerizable compound according to any one of claims 1 to 6. The composition according to claim 7 or 8, comprising 3 to 50 parts by weight of the polymerizable compound according to any one of claims 1 to 6.   An optical film comprising a structural unit derived from the polymerizable compound according to claim 1.   An optical film obtained by polymerizing the composition according to claim 7.   The optical film according to claim 10 or 11, wherein the optical film is a λ / 4 plate showing 113 to 163 nm as a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film. .   The optical film according to claim 10 or 11, wherein the optical film is a λ / 2 plate showing 250 to 300 nm as a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film. .   A polarizing plate comprising the optical film and polarizing film according to claim 10.   A flat panel display comprising the polarizing plate according to claim 14 and a liquid crystal panel.   An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate according to claim 14.   The manufacturing method of the unpolymerized film characterized by including the process of apply | coating the composition in any one of Claims 7-9 to a support base material, and making it dry.   The manufacturing method of the unpolymerized film characterized by including the process of apply | coating and drying the composition in any one of Claims 7-9 on the oriented film formed on the support base material.   The manufacturing method of the optical film characterized by including the process of hardening | curing the unpolymerized film obtained by the manufacturing method of Claim 17 or 18 by superposition | polymerization.

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