Liquid crystal device and liquid crystal apparatus

• US 6,177,152 B1
• Filed: 10/18/1996
• Issued: 01/23/2001
• Est. Priority Date: 10/20/1995
• Status: Expired due to Fees

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Yamada, Syuji, Terada, Masahiro, Sato, Koichi, Shinjo, Kenji
• Primary Examiner(s): KELLY, CYNTHIA HARRIS
• Application Number:
  US08/733,771
• Time in Patent Office: 1,558 Days
• Field of Search: 252/299.01, 252/299.6, 428/1.1, 428/1.26, 349/182, 349/123
• US Class Current: 428/1.1
• CPC Class Codes: C09K 19/0225 Ferroelectric
• CPC Class Codes: C09K 19/04 characterised by the chemical structure of the liquid crystal components , e.g. by a specific unit
• CPC Class Codes: C09K 19/42 Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
• CPC Class Codes: C09K 2323/00 Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
• CPC Class Codes: C09K 2323/027 Polyimide
• CPC Class Codes: G02F 1/133723 Polyimide, polyamide-imide

Abstract

A liquid crystal device having a pair of electrode substrates, and a liquid crystal composition disposed between the substrates. At least one of the substrates is provided with an alignment control layer having a thickness of at most 200 Å and having been subjected to a rubbing uniaxial aligning treatment. The liquid crystal composition contains at least 30 wt. % of (i) at least one species of a fluorine-containing mesomorphic compound (B) represented by a formula (II) having smectic C phase and providing a tilt angle below 30 degrees at a temperature 15° C. below an upper limit temperature of said smectic C phase

(ii) at least one species of compound (C) in an amount at least 5 wt. % represented by the formula (II) having a smectic C phase and which provides a tilt angle of at least 30 degrees at a temperature 15° C. below an upper limit temperature of said smectic C phase.

Claims

1. A liquid crystal device, comprising:

a pair of substrates each having thereon at least an electrode, and a liquid crystal composition disposed between the substrates, wherein at least one of the substrates is provided with an alignment control layer having a thickness of at most 200 Å and

having been subjected to a rubbing uniaxial aligning treatment, and the liquid crystal composition comprises;

(i) at least one species of a fluorine-containing mesomorphic compound (B) represented by a formula (II) comprising at least one catenary oxygen atom, a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core, said compound (B) having smectic C phase and providing a tilt angle below 30 degrees at a temperature 15°

C. below an upper limit temperature of said smectic C phase; and

(ii) at least one species of compound (C) in an amount at least 5 wt. % represented by the formula (II) comprising at least one catenary oxygen atom, a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core and having a smectic C phase and which provides a tilt angle of at least 30 degrees at a temperature 15°

C. below an upper limit temperature of said smectic C phase;

the liquid crystal composition containing said compounds (B) and (C) in a total amount of at least 30 wt. %;

where A⁴, A⁵ and A⁶ are each independently denote

gb, hb and ib are each independently an integer of 0-3 with the proviso that the sum of gb+hb+ib be at least 2;

each L³ and L⁴ are independently a single bond, —

CO—

O—

, —

O—

CO—

, —

CO—

S—

, —

S—

CO—

, —

CO—

Se—

, Se—

CO—

—

CO—

Te—

, —

Te—

CO—

, —

(CH₂CH₂)_ka—

(ka is 1-4), —

CH═

CH—

, —

C≡

C, —

CH═

N—

, —

N═

CH—

, —

CH₂—

O—

, —

O—

CH₂—

, —

CO—

or —

O—

;

X², Y² and Z² are each a substituent of A⁴, A⁵ and A⁶, respectively, and each X₂, Y₂ and Z₂ are independently —

H, —

Cl, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CF₃, —

O—

CF₃, —

CN or —

NO₂;

each jb, mb and nb are independently an integer of 0-4;

J² is —

CO—

O—

C_rcH_2rc—

, —

O—

C_rcH_2rc—

, —

C_rcH_2rc—

, —

O—

(C_saH_2sa—

O)_ta—

C_rdH_2rd—

, —

O—

SO₂—

, —

SO₂—

, —

SO₂—

C_rcH_2rc—

, —

C_rcH_2rc—

N(C_pbH_2pb+1)—

SO₂—

or —

C_rcH_2rc—

N(C_pbH_2pb+1)—

CO—

where rc and rd are independently 1-0;

sa is independently 1-10 for each (C_saH_2sa—

O), ta is 1-6;

pb is 0-4;

—

R⁴ is —

O—

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

C_qcH_2qc—

R⁶, —

O—

C_qcH_2qc—

R⁶, —

CO—

O—

C_qcH_2qc—

R⁶, or O—

CO—

C_qcH_2qc—

R⁶ which may either be straight chain or branched where R⁶ is —

O—

CO—

C_qdH_2qd+1;

—

CO—

O—

C_qdH_2qd+1, —

Cl, —

F, —

CF₃, —

NO₂, —

CN or —

H, qc and qd are independently 1-20;

wa is 1-10; and

R⁵ is (C_xbF_2xb—

O)_za—

C_yaF_2ya+1, where xb is independently 1-10 for each (C_xbF_2xb—

O);

ya is 1-10; and

za is 1-10.

2. The liquid crystal device according to claim 1, wherein said liquid crystal composition further comprises (iii) at least one species of a fluorine containing mesomorphic compound (A) represented by formula (I) or said formula (II) comprising a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core, and having smectic mesophase or latent smectic mesophase

wherein A¹, A² and A³ are each independently

ga, ha and ia are independently an integer of 0-3 with the proviso that the sum of ga+ha+ia be at least 2;

L¹ and L² are independently a covalent bond, —

CO—

O—

, —

O—

CO—

, —

COS—

, —

S—

CO—

, —

CO—

Se—

, —

Se—

CO—

, —

CO—

Te—

, —

Te—

CO—

, —

CH₂CH₂—

, —

CH═

CH—

, —

CE≡

C—

, —

CH═

N—

, —

N═

CH—

, —

CH₂—

O—

, —

O—

CH₂—

, —

CO—

or —

O—

;

X¹, Y¹ and Z¹ are each a substituent of A¹, A² and A³, respectively, and each X¹, Y¹ and Z¹ are independently —

H, —

Cl, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CN or —

NO₂;

each ja, ma and na are independently an integer of 0-4;

J¹ is —

CO—

O—

(CH₂)_ra—

, —

O—

(CH₂)_ra, —

(CH₂)_ra, —

O—

SO₂—

, —

SO₂—

, —

SO₂—

(CH₂)_ra, —

O—

(CH₂)_ra, —

O—

(CH₂)_rb—

, —

(CH₂)ra—

N(C_paH_2pa+1)—

SO₂—

or —

(CH₂)_ra—

N(C_paH_2pa+1)—

CO—

where ra and rb are independently 1-20, and pa is 0-4;

R₁ is —

O—

C_qaH_2qa—

O—

C_qbH_2qb+1, —

C_qaH_2qa—

O—

, C_qbH_2qb+1, —

C_qaH_2qa—

R³, —

O—

C_qaH_2qa—

R³, —

CO—

C_qaH_2qa—

R³, or —

O—

CO—

C_qaH_2qa,—

R₃ which may be either straight chain or branched where R₃ is —

O—

O—

C_qbH_2qb+1, —

CO—

O—

C_qbH_2qb+1, —

H, —

C1, —

F, —

CF3, —

NO₂ or —

CN; and

qa and qb are independently 1-20; and

R₂ is C_xaF_2xa—

X, wherein x is —

H or —

F, xa is an integer of 1-20.

3. A device according to claim 1 or 2, wherein the pair of substrates have been subjected to different aligning treatments.

4. A device according to claim 1 or 2, wherein R⁴ in the formula (II) for compound (C) is —

C—

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

O—

C_qcH_2qc—

R⁶, or O—

CO—

C_qcH_2qc—

R⁶ wherein qc, qd, wa and R⁶ have the meanings defined above.

5. A device according to claim 1 or 2, wherein the fluorine-containing mesomorphic compound (A) of the formula (I) or (II) has a central core containing benzene ring and pyrimidine ring.

6. A device according to claim 1 or 2, wherein the compound (B) of the formula (II) has a central core containing benzene ring and pyrimidine ring.

7. A device according to claim 1 or 2, wherein the liquid crystal composition comprises at least 50 wt. % of the compound (B).

8. A device according to claim 1 or 2, wherein the liquid crystal composition comprises at least 10 wt. % of the compound (C).

9. A device according to claim 1 or 2, wherein said tilt angle provided by the compound (C) is at least 35 degrees.

10. A device according to claim 1 or 2, wherein said alignment control layer has a thickness of at least 100 Å

.

11. A device according to claim 1 or 2, wherein said alignment control layer has a thickness of at most 50 Å

.

12. A device according to claim 1 or 2, wherein said alignment control layer comprises a polyimide film.

22. A liquid crystal apparatus, including a liquid crystal device according to any one of claims 1, 2, 13 or 14.

13. A liquid crystal device, comprising:

a pair of substrates each having thereon at least an electrode, and a liquid crystal composition disposed between the substrates, wherein at least one of the substrates is provided with an alignment control layer comprising a polyimide film, and the liquid crystal composition comprises;

(i) at least one species of a fluorine-containing mesomorphic compound (B) represented by a formula (II) comprising at least one catenary oxygen atom, a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core, said compound (B) having smectic C phase and providing a tilt angle below 30 degrees at a temperature 15°

C. below an upper limit temperature of said smectic C phase; and

(ii) at least one species of compound (C) in an amount at least 5 wt. % represented by the formula (II) comprising at least one catenary oxygen atom, a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core and having a smectic C phase and which provides a tilt angle of at least 30 degrees at a temperature 15°

C. below an upper limit temperature of said smectic C phase;

the liquid crystal composition containing said compounds (B) and (C) in a total amount of at least 30 wt. %.

where A⁴, A⁵ and A⁶ are each independently denote

gb, hb and ib are each independently an integer of 0-3 with the proviso that the sum of gb+hb+ib be at least 2;

each L³ and L⁴ are independently a single bond, —

CO—

O—

, —

O—

CO—

, —

CO—

S—

, —

S—

CO—

, —

CO—

Se—

, Se—

CO—

—

CO—

Te—

, —

Te—

CO—

, —

(CH₂CH₂)_ka—

(ka is 1-4), —

CH═

CH—

, —

C≡

C, —

CH═

N—

, —

N═

CH—

, —

CH₂—

O—

, —

O—

CH₂—

, —

CO—

or —

O—

;

X², Y² and Z² are each a substituent of A⁴, A⁵ and A⁶, respectively, and each X₂, Y₂ and Z₂ are independently —

H, —

C1, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CF₃, —

O—

CF₃, —

CN or —

NO₂;

each jb, mb and nb are independently an integer of 0-4;

J² is —

CO—

O—

C_rcH_2rc—

, —

O—

C_rcH_2rc—

, —

C_rcH_2rc—

, —

O—

(C_saH_2sa—

O)_ta—

C_rdH_2rd—

, —

O—

SO₂—

, —

SO₂—

, —

SO₂—

C_rcH_2rc—

, —

C_rcH_2rc—

N(C_pbH_2pb+1)—

SO₂—

or —

C_rcH_2rc—

N(C_pbH_2pb+1)—

CO—

where rc and rd are independently 1-0;

sa is independently 1-10 for each (C_saH_2sa—

O), ta is 1-6;

pb is 0-4;

—

R⁴ is —

O—

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

C_qcH_2qc—

R⁶, —

O—

C_qcH_2qc—

R⁶, —

CO—

O—

C_qcH_2qc—

R⁶, or O—

CO—

C_qcH_2qc—

R⁶ which may either be straight chain or branched where R⁶ is —

O—

CO—

C_qdH_2qd+1, —

CO—

O—

C_qdH_2qd+1, —

C1, —

F, —

CF₃, —

NO₂, —

CN or —

H, qc and qd are independently 1-20;

wa is 1-10; and

R⁵ is (C_xbF_2xb—

O))_za—

C_yaF_2ya+1, where xb is independently 1-10 for each (C_xbF2xb—

O);

ya is 1-10; and

za is 1-10.

14. The liquid crystal device according to claim 13, wherein said liquid crystal composition further comprises (iii) at least one species of a fluorine containing mesomorphic compound (A) represented by formula (I) or said formula (II) comprising a fluorocarbon terminal portion and a hydrocarbon terminal portion, the terminal portions being connected with a central core, and having smectic mesophase or latent smectic mesophase

wherein A¹, A² and A³ are each independently

ga, ha and ia are independently an integer of 0-3 with the proviso that the sum of ga+ha+ia be at least 2;

L¹ and L² are independently a covalent bond, —

CO—

O—

, —

O—

CO—

, —

COS—

, —

S—

CO—

, —

CO—

Se—

, —

Se—

CO—

, —

CO—

Te—

, —

Te—

CO—

, —

CH₂CH₂—

, —

CH═

CH—

, —

C≡

C—

, —

CH═

N—

, —

N═

CH—

, —

CH₂—

O—

, —

O—

CH₂—

, —

CO—

or —

O—

;

X¹, Y¹ and Z¹ are each a substituent of A¹, A² and A³, respectively, and each X¹, Y¹ and Z¹ are independently —

H, —

C1, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CN or —

NO₂;

each ja, ma and na are independently an integer of 0-4;

J¹ is —

CO—

O—

(CH₂)_ra—

, —

O—

(CH₂)_ra—

, —

(CH₂)_ra—

, —

O—

SO₂—

, —

SO₂—

, —

SO₂—

(CH₂)_ra—

, —

O—

(CH₂)_ra, —

O—

(CH₂)_rb—

, —

(CH₂) ra—

N(C_paH_2pa+1)—

SO₂—

or —

(CH₂)_ra—

N(C_paH_2pa+1)—

CO—

where ra and rb are independently 1-20, and pa is 0-4;

R₁ is —

O—

C_qaH_2qa—

O—

C_qbH_2qb+1, —

C_qaH_2qa—

O—

, C_qbH_2qb+1, —

C_qaH_2qa, —

R³, —

O—

C_qaH_2qa—

R³, —

CO—

C_qaH_2qa—

R³, or —

O—

CO—

C_qaH_2qa—

R₃ which may be either straight chain or branched where R₃ is —

O—

CO—

C_qbH_2qb+1, —

CO—

O—

C_qbH_2qb+1, —

H, —

C1, —

F, —

CF3, —

NO₂ or —

CN; and

qa and qb are independently 1-20; and

R² is C_xaF_2xa—

X, wherein X is —

H or —

F, xa is an integer of 1-20.

15. A device according to claim 13 or 14, wherein said polyimide has a recurring unit represented by the following formula (III):

in which

K is

L¹¹ and L¹² independently denote

or an alkylene group having 1-20 carbon atoms;

M¹¹is a single bond or —

O—

; and

a is 0, 1 or 2.

16. A device according to claim 13 or 14, wherein the pair of substrates have been subjected to different aligning treatments.

17. A device according to claim 13 or 14, wherein R⁴ in the formula (II) for compound (C) is —

O—

(C_qcH_2qc—

O)_wa—

C_qdH_2qd+1, —

O—

C_qcH_2qc—

R⁶, or O—

CO—

C_qcH_2qc—

R⁶ wherein qc, qd, wa and R⁶ have the meanings defined above.

18. A device according to claim 13 or 14, wherein the compound (B) of the formula (II) has a central core containing benzene ring and pyrimidine ring.

19. A device according to claim 13 or 14, wherein the liquid crystal composition comprises at least 50 wt. % of the compound (B).

20. A device according to claim 13 or 14, wherein the liquid crystal composition comprises at least 10 wt. % of the compound (C).

21. A device according to claim 13 or 14, wherein said tilt angle provided by the compound (C) is at least 35 degrees.