TWI771683B - Photoreactive liquid crystal composition, dimming element, and manufacturing method of dimming element - Google Patents

Abstract

The present invention provides an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a dimming element and/or a photoreactive liquid crystal for manufacturing the element composition. The present invention provides (A) a photoreactive polymer having a photoreactive side chain that generates at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization The photoreactive liquid crystal composition of liquid crystal; and (B) low molecular liquid crystal; and the weight ratio ((A) component: (B) component) of the (A) component and (B) component is 3:97~20: A composition of 80 and a dimming element formed with a liquid crystal cell containing the composition.

Description

Photoreactive liquid crystal composition, dimming element, and method for producing the dimming element

The present invention relates to a photoreactive liquid crystal composition, a dimming element formed with the photoreactive liquid crystal composition, and a method for manufacturing the dimming element.

Current liquid crystal display elements, in addition to some elements such as polymer dispersed liquid crystal (PDLC), use a liquid crystal alignment film after an alignment treatment in order to align the liquid crystal uniformly (Non-Patent Document 1). ). The alignment treatment of the liquid crystal alignment film is a method of rubbing the surface of the film with a roller of a winding cloth, which is generally called a rubbing treatment after coating the liquid crystal alignment film. There is a problem in that the display performance of the liquid crystal display element is lowered due to damage or chips caused. In addition, this alignment treatment must go through many steps, such as a liquid crystal alignment film formation step, a liquid crystal alignment treatment step, and a cleaning step of the liquid crystal alignment film, which complicates the manufacturing steps.

Therefore, without using the liquid crystal alignment film, a liquid crystal cell capable of controlling the alignment of the liquid crystal can be produced, which has great advantages in terms of process and cost.

In addition, PDLC is a technique in which a liquid crystal cell is produced using a low molecular liquid crystal in which a photoreactive polymerizable compound is mixed in advance, and then, the polymerizable compound is polymerized by irradiating ultraviolet rays from outside the cell to fix the liquid crystal. However, the present technology does not apply the alignment treatment of the liquid crystal, so the alignment of the liquid crystal is not controlled. When the device is applied to a dimming device or a display device, there is a problem of insufficient electro-optical properties (for example, refer to Non-Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-201388.

[Patent Document 2] Japanese Patent Laid-Open No. 2003-307720.

[Non-patent literature]

[Non-Patent Document 1] Liquid Crystal Fact Sheet Maruzen Corporation.

[Outline of Invention]

Therefore, the object of the present invention is to provide an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a dimming element and/or a device for manufacturing the element. Photoreactive liquid crystal composition.

Furthermore, in addition to or in addition to the above-mentioned object, an object of the present invention is to provide an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, and specifically a method of manufacturing a light-adjusting element.

The present inventors discovered the following invention.

<1> A photoreactive liquid crystal composition having

(A) a photoreactive polymer liquid crystal having at least one photoreactive side chain selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization; and (B) ) low molecular liquid crystal; the photoreactive liquid crystal composition,

The weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) low molecular weight liquid crystal) is 3:97~20:80, preferably 4 : 96~15:85, more preferably 5:95~13:87.

<2> A photoreactive liquid crystal composition having

(A) a photoreactive polymer liquid crystal having at least one photoreactive side chain selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization; and (B) ) low molecular liquid crystal; the photoreactive liquid crystal composition,

By exposing the composition to polarized ultraviolet rays, and heating the composition to a temperature 50°C lower than the lower limit of the temperature range in which the (A) photoreactive polymer liquid crystal exhibits liquid crystallinity, preferably 65 to 150°C °C, more preferably 70 to 120 °C, so that the (B) low-molecular-weight liquid crystal can have a specific orientation.

<3> In the above <1>, it is obtained by exposing the composition to polarized ultraviolet rays and heating the composition to a temperature that is 50 degrees lower than the lower limit of the temperature range in which the (A) photoreactive polymer liquid crystal exhibits liquid crystallinity above the temperature of ℃, preferably It is 65-150 degreeC, More preferably, it is 70-120 degreeC, and (B) low molecular liquid crystal can have specific orientation.

<4> In any one of the above <1> to <3>, the (A) photoreactive polymer liquid crystal may have a photoreactive side chain that generates (A-1) photocrosslinking reaction.

<5> In any one of the above <1> to <4>, (A) the photoreactive polymer liquid crystal may have a structure selected from the following formulae (1) to (6)

(In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-;

S is an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them can also be substituted by a halogen group;

T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them can also be substituted by a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms, or a substituent selected from them. The same or different 2~6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents hydrogen atom or carbon number. 1~5 alkyl group), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, carbon number 1~5 alkyl group, or carbon number 1~5 Alkyloxy substitution;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with a carbon number of 5 to 8, and a combination thereof, and is bonded to it. The same hydrogen atoms can be independently replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Alkyloxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, or the same definition as Y ₁ ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them can each independently also be replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1-5 carbon atoms, or alkyloxy group with 1-5 carbon atoms;

q1 and q2, one of which is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; but When X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side of the -CH=CH- bond is an aromatic ring, and when the number of P is 2 or more, P may be the same or different from each other, and when the number of Q becomes 2 or more, Q may be the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When l1 and 12 are 0 at the same time, when T is a single bond, A also means a single bond;

When l1 is 1, when T is a single bond, B also means a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof)

Photoreactive side chains of any of the groups.

<6> In any one of the above <1> to <5>, (A) the photoreactive polymer liquid crystal may have a formula selected from the following formulas (7) to (10)

(In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms, or the same or different substituents selected from them The 2~6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 5. alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms replace;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

l represents an integer from 1 to 12;

m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3;

n represents an integer from 0 to 12 (but when n=0, B is a single bond);

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with a carbon number of 5 to 8, and a combination thereof, and is bonded to it. The same hydrogen atoms can be independently replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Alkyloxy substitution;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ )

Photoreactive side chains of any of the groups.

<7> In any one of the above <1> to <5>, (A) high photoreactivity The molecular liquid crystal may have a formula selected from the following formulas (11) to (13)

(In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or - O-CO-CH=CH-;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

l represents an integer from 1 to 12, m represents an integer from 0 to 2, and m1 represents an integer from 1 to 3;

R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different substituents selected from them. The bases formed by the rings of 2 to 6 are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbon atoms. base), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms. , or represents a hydroxyl group or an alkoxy group with 1 to 6 carbon atoms)

Photoreactive side chains of any of the groups.

<8> In any one of the above <1> to <5>, (A) the photoreactive polymer liquid crystal may have the following formula (14) or (15)

(In the formula, A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or - O-CO-CH=CH-;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms, or the same or different substituents selected from them The 2~6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 5. alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms replace;

l represents an integer from 1 to 12, and m1 and m2 represent an integer from 1 to 3)

Indicates the photoreactive side chain.

<9> In any one of the above <1> to <5>, (A) the photoreactive polymer liquid crystal may have the following formula (16) or (17) (wherein A represents a single bond, -O- , -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

l represents an integer from 1 to 12, and m represents an integer from 0 to 2)

Indicates the photoreactive side chain.

<10> In any one of the above <1> to <5>, (A) the photoreactive polymer liquid crystal may have the following formula (20) (wherein A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms, or the same or different substituents selected from them The 2~6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 5. alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms replace;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

l represents an integer from 1 to 12, and m represents an integer from 0 to 2) to represent the photoreactive side chain.

<11> A light-adjusting element formed by having a liquid crystal cell containing the photoreactive liquid crystal composition according to any one of the above items <1> to <10>.

<12> A dimming element comprising a liquid crystal cell containing the photoreactive liquid crystal composition according to any one of the above items <1> to <10>, wherein, in the liquid crystal cell, (B ) Low molecular liquid crystals have specific orientation.

<13> A method of manufacturing a dimming element, which comprises the following steps [I] to [III] to form (B) a dimming element with a low-molecular-weight liquid crystal having specific alignment in a liquid crystal cell,

[I] A photoreactive polymer having (A) a photoreactive side chain having at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization Liquid crystal; and (B) the photoreactive liquid crystal composition of low molecular liquid crystal; filling the space formed between two transparent substrates arranged in parallel and separated, to form a liquid crystal cell;

[II] The step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from either of the two transparent substrates;

[III] By heating the liquid crystal cells to a temperature that is 50°C lower than the lower limit of the temperature range in which the (A) photoreactive polymer liquid crystal exhibits liquid crystallinity, preferably 65 to 150°C, more preferably 70 to 120°C °C steps.

<14> In the above-mentioned <13>, the step [III] may be performed in the step [II].

<15> In the above-mentioned <13> or <14>, the step [III] may be performed after the step [II].

<16> In any one of the above <13> to <15>, the weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) Low molecular liquid crystal) is 3:97~20:80, preferably 4:96~15:85, more preferably 5:95~13:87.

<17> In any one of the above-mentioned <13> to <16>, (A) the photoreactive polymer liquid crystal may have a photoreactive side chain that generates (A-1) photocrosslinking reaction.

<18> In any one of the above <13> to <17>, (A) the photoreactive polymer liquid crystal may have a compound selected from the above formulae (1) to (6) (in the formula, A, B, D, S , T, Y ₁ , Y ₂ , R, X, Cou, q1 , q2 , q3 , P, Q, 11 , 12 , H and I have the same definitions as above) the photoreactive side chain of any one of the groups .

<19> In any one of the above <13> to <18>, (A) the photoreactive polymer liquid crystal may have a compound selected from the above formulae (7) to (10) (in the formula, A, B, D, Y ₁ , X, 1, m, m1, m2, n, _Y2 and R are photoreactive side chains of any one of the groups having the same definitions as above).

<20> In any one of the above <13> to <18>, (A) the photoreactive polymer liquid crystal may have a compound selected from the above formulae (11) to (13) (wherein A, X, l, m , m1 and R are photoreactive side chains of any one grouped by the same definition as above).

<21> In any one of the above <13> to <18>, (A) the photoreactive polymer liquid crystal may have the above formula (14) or (15) (wherein A, Y ₁ , l, m1 and m2 is a photoreactive side chain having the same definition as above).

<22> In any one of the above <13> to <18>, (A) the photoreactive polymer liquid crystal may have the above formula (16) or (17) (in the formula, A, X, l and m have The same definition as above) represents the photoreactive side chain.

<23> In any one of the above <13> to <18>, (A) the photoreactive polymer liquid crystal may have the above formula (20) (in the formula, A, Y ₁ , X, l and m have The same definition as above) represents the photoreactive side chain.

The present invention can provide an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a dimming element and/or a photoreactive liquid crystal composition for making the element. .

Furthermore, in addition to the above-mentioned effects or the above-mentioned effects, the present invention can provide an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a method of manufacturing a light-adjusting element.

1: Liquid Crystal Cell

2: Ultraviolet light emitting part

3,13: Polarizer

4,16: Sample

5: sample table

6: Temperature Control Department

11: Experimental Department

12: He-Ne Laser

14: Analyzer

15: Power meter measuring instrument

Fig. 1 shows an example of an ultraviolet irradiation apparatus for producing the light-adjusting element of the present invention.

2 is a schematic diagram showing an experimental system for measuring the intensity of transmitted diffracted light in liquid crystal cells obtained after polarized light exposure in Examples and Comparative Examples.

[ Fig. 3 ] In the experimental system shown in Fig. 2 , the transmission measured when the liquid crystal cells of Example 1, Comparative Example 2, and Comparative Example 3 were rotated (horizontal axis: angle) Results of light intensity (vertical axis).

4 shows the results of measuring the transmitted light intensity (vertical axis) when the liquid crystal cells of Example 2, Comparative Example 4, and Comparative Example 5 were rotated (horizontal axis: angle) in the experimental system shown in FIG. 2 .

The present application provides an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a dimming element and/or a photoreactive liquid crystal composition for manufacturing the element.

Moreover, the present application provides an element obtained by controlling the alignment of a liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, and specifically, a method for producing a light-adjusting element.

Hereinafter, a photoreactive liquid crystal composition, a device obtained from the composition, specifically a light-adjusting device, and a method for producing the device will be described.

<Photoreactive Liquid Crystal Composition>

The photoreactive liquid crystal composition of the present invention has (A) a photoreactive side chain having at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization. photoreactive high molecular liquid crystal; and (B) low molecular liquid crystal.

The photoreactive liquid crystal composition of the present invention may be composed of only (A) photoreactive polymer liquid crystal; and (B) low molecular liquid crystal; Consists of (A) and (B) of the other ingredients to such an extent that their properties remain unchanged. In addition, the photoreactive liquid crystal composition of the present invention does not include (A) or In addition to (B), other components may be contained.

<<(B) Low molecular liquid crystal>>

The (B) low-molecular-weight liquid crystal contained in the photoreactive liquid crystal composition of the present invention can be used as it is, such as nematic liquid crystal (Nematic LC), ferroelectric liquid crystal, and the like conventionally used in liquid crystal display elements.

Specifically, as (B) low-molecular-weight liquid crystals, for example, cyanobiphenyls such as 4-cyano-4'-n-pentylbiphenyl and 4-cyano-4'-n-heptyloxybiphenyl can be mentioned. Cholesterol esters such as cholesterol acetate and cholesterol benzoate; carbonates such as 4-carboxyphenylethyl carbonate and 4-carboxyphenyl-n-butyl carbonate; phenyl benzoate , Phenyl esters such as biphenyl phthalate; Schiff bases such as benzylidene-2-naphthylamine, 4'-n-butoxybenzylidene-4-acetylaniline, etc. : Benzidines such as N,N'-bisbenzylidenebenzidine, p-dianisylbenzidine, etc.; 4,4'-azodiphenyl oxide, 4,4'-di-n-butoxy Azobenzene oxides such as azobenzene oxide; liquid crystals of phenylcyclohexyl system, terphenyl system, phenylbicyclohexyl system, etc. specifically shown below; etc., but not limited to these.

<<(A) Photoreactive Polymer Liquid Crystal>>

The (A) photoreactive polymer liquid crystal (hereinafter referred to as "component (A)" in some cases) contained in the photoreactive liquid crystal composition of the present invention may have a photointeraction selected from the group consisting of (A-1). In the case of linking and (A-2) the photoreactive side chain of at least one kind of reaction formed by photoisomerization, it is not particularly limited.

In this specification, photoreactivity refers to the property of generating either reaction of (A-1) photocrosslinking or (A-2) photoisomerization; and a reaction of both.

It is preferable that (A) component has the side chain which generate|occur|produces the photocrosslinking reaction of (A-1).

The component (A) is a polymer exhibiting liquid crystallinity in i) a specific temperature range, and a polymer having a photoreactive side chain.

The component (A) may react with light in the wavelength range of ii) 250 nm to 400 nm and exhibit liquid crystallinity in the temperature range of 50 to 300°C.

(A) Component has one of the wavelengths in the range of iii) 250nm to 400nm The photoreactive side chain which reacts with light, especially polarized ultraviolet rays, is preferable.

Component (A) exhibits liquid crystallinity in the temperature range of iv) 50 to 300°C, so it is preferable to have a liquid crystal group.

In the photoreactive liquid crystal composition of the present invention, the weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) low molecular weight liquid crystal) is 3 : 97~20:80, preferably 4:96~15:85, more preferably 5:95~13:87.

(A): When the ratio of (A) in (B) is within the above range, i) the amount of alignment groups necessary for liquid crystal alignment can be secured, ii) uniform liquid crystal alignment can be obtained, and iii) photoreactivity can be obtained The polymer liquid crystal (A) reacts with polarized ultraviolet rays and the density of the polymer matrix becomes a desired value, and iv) the low molecular liquid crystal (B) responds as expected when a voltage is applied. good.

(A) Component contains the photoreactive side chain which has photoreactivity as mentioned above. The structure of the side chain is not particularly limited, but it is preferable to have a structure that causes the reaction shown in the above (A-1) and/or (A-2), and a structure that causes the photocrosslinking reaction (A-1) . (A-1) The structure of the photocrosslinking reaction is preferable because the orientation of the component (A) can be stably maintained for a long period of time even if the structure after the reaction is exposed to external stress (EXTERNAL STRESS) such as heat.

The structure of the side chain of the component (A) has a rigid liquid crystal (mesogenic) component, and the alignment of the liquid crystal is stable, which is preferable.

The liquid crystal component includes, for example, biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, and the like, but is not limited to and so on.

The structure of the main chain of the component (A) is, for example, selected from hydrocarbons, (meth)acrylates, iconate esters, fumarate esters, maleate esters, α-methylene-γ-butyrolactone , at least one of the group of radical polymerizable groups such as styrene, ethylene (vinyl), maleimide, norbornene, and siloxane, but not limited to these.

Moreover, it is preferable that the side chain of (A) component is a side chain which consists of at least 1 type of following formula (1)-(6).

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ - , -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , or -O-CO-CH=CH-;

S is an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them can also be substituted by a halogen group;

T is a single bond or an alkylene group with 1 to 12 carbon atoms, and the hydrogen atom bonded to them can also be substituted by a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms, or the same or different substituents selected from them The 2~6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to them can also be independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 5. alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms replace;

Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with a carbon number of 5 to 8, and a combination thereof, and is bonded to it. The same hydrogen atoms can be independently replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Alkyloxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, or the same definition as Y ₁ ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -, when the number of X becomes 2, X can be the same or different from each other;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them can each independently also be replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= CH-CN, halogen group, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms;

q1 and q2, one of which is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof; but When X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side of the -CH=CH- bond is an aromatic ring, and when the number of P is 2 or more, P may be the same or different from each other, and when the number of Q becomes 2 or more, Q may be the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When l1 and 12 are 0 at the same time, when T is a single bond, A also means a single bond;

When l1 is 1, when T is a single bond, B also means a single bond;

H and I are each independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

The side chain may be selected from any photoreactive side chain grouped by the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above;

l represents an integer from 1 to 12;

m represents an integer from 0 to 2, and m1 and m2 represent an integer from 1 to 3;

n represents an integer from 0 to 12 (but when n=0, B is a single bond).

The side chain may be any photoreactive side chain selected from the group of the following formulae (11) to (13).

In the formula, A, X, l, m, m1 and R have the same definitions as above.

The side chain may be a photoreactive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

The side chain may be a photoreactive side chain represented by the following formula (16) or (17).

In the formula, A, X, l and m have the same definitions as above.

The side chain may be a photoreactive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, l and m have the same definitions as above.

Moreover, (A) component may have any liquid crystalline side chain selected from the group of following formula (21)-(31). For example, when the photoreactive side chain of the component (A) does not have liquid crystallinity, or when the main chain of the component (A) does not have liquid crystallinity, the component (A) may be selected from the following formulas (21) to ( 31) made A liquid crystal side chain of any of the groups.

In the formula, A, B, q1 and q2 have the same definitions as above;

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon with a carbon number of 5 to 8, and a combination thereof, and a bond Each of the hydrogen atoms bound to them can be independently substituted by -NO ₂ , -CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms;

R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing ring Heterocycle, alicyclic hydrocarbon with carbon number 5-8, alkyl group with carbon number 1-12, or alkoxy group with carbon number 1-12;

l represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in equations (23) to (24), the sum of all m is 2 or more, and in equations (25) to (26), all m The total is 1 or more, and m1, m2 and m3 each independently represent an integer from 1 to 3;

R ₂ represents, a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl, or alkyloxy;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<<(A) Component preparation method>>

(A) Component can be obtained by adding the photoreactive side chain of the above-mentioned photoreactive It may be obtained by polymerizing a side chain monomer, and may be obtained by copolymerizing the photoreactive side chain monomer and a monomer having the above-mentioned liquid crystal side chain.

[Photoreactive side chain monomer]

The photoreactive side chain monomer system refers to a monomer capable of forming a polymer having a photoreactive side chain in the side chain portion of the polymer when forming a polymer in this specification.

The photoreactive group possessed by the side chain is preferably the following structures and derivatives thereof.

More specific examples of the photoreactive side chain monomers include, for example, compounds selected from the group consisting of hydrocarbons, (meth)acrylates, iconic acid esters, fumaric acid esters, maleic acid esters, α-methylene-γ - A polymerizable group consisting of a radically polymerizable group such as butyrolactone, styrene, ethylene, maleimide, norbornene, and at least one of siloxane groups, and a polymerizable group composed of the above formula (1 The photoreactive side chain composed of at least one of ) to (6) is preferably, for example, a photoreactive side chain composed of at least one of the above formulas (7) to (10). )~(13) constituted by at least one photoreactive side chain, the photoreactive side chain represented by the above formula (14) or (15), the photoreactive side chain represented by the above formula (16) or (17) The structure of the chain and the photoreactive side chain represented by the above formula (20) is preferable.

Examples of the photoreactive side chain monomers include the following formulae PRM-1 to PRM-11 (wherein, n represents an integer of 1 to 6, m represents an integer of 0 to 4, X represents a hydrogen atom or a methyl group, and R represents Hydrogen atom, linear or branched alkyl or alkoxy group with 1 to 3 carbon atoms, halogen atom, cyano group, or nitro group, R ₁ to R ₃ each independently represent a hydrogen atom, a straight chain with 1 to 3 carbon atoms A compound represented by a chain or branched alkyl group or an alkoxy group, or a halogen atom, p represents an integer of 1 to 4), but is not limited thereto.

[Liquid crystal side chain monomer]

The liquid crystal side chain monomer system refers to a monomer derived from the monomer which exhibits liquid crystallinity, and which can form a liquid crystal group at the side chain site of the polymer in this specification.

The liquid crystal group possessed by the side chain may be a group such as biphenyl or phenyl benzoate, which forms a liquid crystal structure alone, or may be a group such as benzoic acid, and the side chains form hydrogen bonds with each other to form a liquid crystal structure group. The liquid crystal group possessed by the side chain preferably has the following structure.

More specific examples of the liquid crystalline side chain monomers include, for example, compounds selected from the group consisting of hydrocarbons, (meth)acrylates, iconic acid esters, fumaric acid esters, maleic acid esters, α-methylene-γ- A polymerizable group consisting of a radical polymerizable group such as butyrolactone, styrene, ethylene, maleimide, norbornene, etc., and at least one of siloxane groups, and a polymerizable group represented by the above formula (21) The structure of the side chain constituted by at least one of ~(31) is preferable.

Specifically, the liquid crystal side chain monomers include, for example, the following formulae LCM-1 to LCM-9 (wherein, n represents an integer of 1 to 6, X represents a hydrogen atom or a methyl group, R ₄ , R ₆ and R ₆₁ to R ₆₃ each independently represent a hydrogen atom, a linear or branched alkyl group or an alkoxy group with a carbon number of 1 to 3, a halogen atom, a cyano group, or a nitro group, and R ₅ represents a hydrogen atom and a carbon number of 1 to 6 The compound represented by the straight-chain or branched-chain alkyl group), but not limited thereto.

(A) Component can be obtained by the polymerization reaction of the photoreactive side chain monomer which exhibits the said liquid crystallinity. In addition, the copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystal side chain monomer or the copolymerization of a photoreactive side chain monomer exhibiting liquid crystallinity and a liquid crystal side chain monomer can be used. And get. In addition, within the range that does not impair the display energy of liquid crystallinity, it can also be combined with other Monomer copolymerization.

As other monomers, for example, commercially available radical polymerizable monomers can be exemplified.

Specific examples of other monomers include, for example, unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like.

The acrylate compound includes, for example, methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthracenyl methacrylate, phenyl acrylate, 2,2,2-Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate , 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantane acrylic acid ester, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc.

The methacrylate compound includes, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and anthracene methacrylate. methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2 methacrylate -Methoxyethyl ester, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, Tetrahydrofurfuryl methyl Acrylate, 3-Methoxybutyl methacrylate, 2-Methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8- Tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like. Glycidol (meth)acrylate, (3-methyl-3-oxocyclobutyl)methyl (meth)acrylate and (3-ethyl-3-oxocyclobutyl)methacrylate can also be used A (meth)acrylate compound having a cyclic ether group such as a base (meth)acrylate.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

As a styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

Maleimide compounds include, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The production method of the side chain type polymer of the present embodiment is not particularly limited, and a general industrial method can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization of a liquid crystal side chain monomer or a photoreactive side chain monomer using a vinyl group. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control and the like.

As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-cleavage type chain transfer (RAFT) polymerization reagents can be used.

Radical thermal polymerization initiators are prepared by heating to the decomposition temperature The above are compounds that generate radicals. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide , benzyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl) base peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxy base neodecanoic acid-tert-butyl ester, peroxytrimethyl acetate-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-pentyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.), etc. Such radical thermal polymerization initiators may be used alone or in combination of two or more.

When the radical photopolymerization initiator is a compound that starts radical polymerization by light irradiation, it is not particularly limited. Such radical photopolymerization initiators include, for example, benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, and thioxanthone , Isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl- 4'-Isopropyl Propiophenone, 1-Hydroxycyclohexyl phenyl ketone, Isopropyl Benzene ether, Isobutyl phenyl acetone, 2,2-diethoxyacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylamine isoamyl benzoate, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-Tris(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2-(4'-methyl) Oxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl) Methyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'- Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) -s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl) yl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2 -(p-Dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4- Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5 ,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1 ,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)- 9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-( 1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'- Tetrakis(t-hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3 ,4'-bis(methoxycarbonyl)-4,3'-bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3' -Di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)- 1-Naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzyl)ethanone, etc. . These compounds may be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, or the like can be used.

The production reaction of the component (A), specifically, the organic solvent used for the polymerization reaction of the above-mentioned monomers is not particularly limited as long as it dissolves the produced polymer. Specific examples thereof are listed below.

N,N-Dimethylformamide, N,N-Dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactamide, Methylidene, Tetramethylurea, Pyridine, Dimethylarne, Hexamethylidene, γ -Butyrolactone, Isopropanol, Methoxymethylpentanol, Dipentene, Ethyl Amyl Ketone , methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellulose, ethyl cellulose, methyl cellosolve acetate, ethyl cellosolve Vegetarian acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol mono Acetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n -Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Oxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, Diglyme, 4-hydroxy-4-methyl yl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N - Dimethylpropionamide, etc.

These organic solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve the produced polymer, as long as the produced polymer does not precipitate, you may mix and use it with the said organic solvent.

In addition, in the case of radical polymerization, oxygen in the organic solvent may inhibit the polymerization reaction, so it is preferable to use the organic solvent that has been degassed as much as possible.

The polymerization temperature in the radical polymerization can be selected at any temperature from 30°C to 150°C, preferably in the range of 50°C to 100°C. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making it difficult to uniformly stir Therefore, the monomer concentration is preferably 1 to 50 mass %, more preferably 5 to 30 mass %. The initial stage of the reaction can be carried out at a high concentration, and then, an organic solvent can be added.

In the above-mentioned radical polymerization reaction, the radical polymerization initiator The ratio of the free radical initiator relative to the monomer to be polymerized is preferably 0.1 relative to the monomer, the molecular weight of the polymer obtained becomes smaller, and the molecular weight of the polymer obtained becomes larger. Molar% ~ 10 Molar%. During further polymerization, various monomer components, solvents, initiators, and the like may be added.

[Recycling of Polymers]

When the product obtained by the above-mentioned reaction, that is, the component (A), is recovered from the reaction solution, the reaction solution can be put into a weak solvent.

Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, heptane, butyl cylosol, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. , methyl ethyl ether, water, etc.

Put it into a weak solvent, and after the precipitated polymer is recovered by filtration, it can be dried at room temperature or by heating under normal pressure or reduced pressure. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the weak solvent in this case include alcohols, ketones, hydrocarbons, and the like. When three or more types of weak solvents selected from these are used, the purification efficiency can be further improved, which is preferable.

The molecular weight of the component (A) of the present invention is the weight-average molecular weight measured by GPC (Gel Permeation Chromatography) method, preferably 2,000-1,000,000, more preferably 5,000-200,000.

As mentioned above, the photoreactive liquid crystal composition of this invention may have other components other than (A) component or (B) component.

Other components depend on the use of (A) component and (B) component, and the use of the photoreactive liquid crystal composition, and examples thereof include hindered amines and hindered phenols. Antioxidants such as the like, or polymerizable compounds having photopolymerizable or photocrosslinked groups at one or more terminals.

Specific examples of the polymerizable compound include, for example, the compounds shown below (in the formula, V is a single bond or -R ₈ O-, preferably -R ₈ O-, and R ₈ has 1 to 10 carbon atoms) , preferably a straight-chain or branched alkyl group with carbon number 2~6. W is a single bond or -OR ₉ -, preferably -OR ₉ -, R ₉ represents carbon number 1~10, preferably It is preferably a straight-chain or branched alkyl group with 2 to 6 carbon atoms. V and W can be the same structure or can be different, and when they are the same, the synthesis is easy. R ₇ represents H or an alkane with 1 to 4 carbon atoms. base), but not so limited.

<A device obtained from a photoreactive liquid crystal composition and its manufacturing method>

The present application also provides a dimming element obtained from the above-mentioned photoreactive liquid crystal composition, and a method for manufacturing the same.

The device of the present invention is formed by having a liquid crystal cell containing the above-mentioned photoreactive liquid crystal composition.

The device of the present invention can be formed by filling the above-mentioned photoreactive liquid crystal composition in a liquid crystal cell.

Specifically, the device of the present invention can be manufactured by the following steps.

By having the following steps [I]~[II], the device of the present invention can be formed, specifically a dimming device, specifically, (B) low molecular liquid crystals with specific alignment are formed in the liquid crystal cells. element, specifically a dimming element.

[I] A photoreactive polymer having (A) a photoreactive side chain having at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization Liquid crystal; and (B) the photoreactive liquid crystal composition of low molecular liquid crystal; filling the space formed between two transparent substrates arranged in parallel and separated, to form a liquid crystal cell;

[II] The step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from either of the two transparent substrates.

The step [I] is the step of forming a liquid crystal cell by filling the above-mentioned photoreactive liquid crystal composition into the space between the transparent substrates by filling the substrates arranged in parallel and separated at least on the side irradiated with ultraviolet rays.

The liquid crystal cell is formed by separating two sheets of transparent substrates to some extent and arranging them in parallel to form a space, and filling the space with the photoreactive composition.

The substrate can use plastic such as glass; acrylic or polycarbonate, etc. Wait. Depending on the element being formed, the base system can also be flexible.

The base system depends on the element to be formed, and various films can also be formed on the space side, such as polyvinyl alcohol, polyether, polyethylene, PET, polyamide, polyimide, acrylic, polycarbonate, polyurea, etc. formed film. In addition, the film used here may have, for example, the following functions. That is, in the step [II] described later, in order to initiate the photoreaction of the (A) photoreactive polymer liquid crystal, the (A) photoreactive polymer liquid crystal can be arranged in the liquid crystal cell, so that the (A) photoreactive polymer liquid crystal can be placed in the liquid crystal cell. The molecular long axis of the reactive polymer liquid crystal absorbs polarized light. In addition, (A) the photoreactive polymer liquid crystal is enclosed in the liquid crystal cell with the composition of (B) the low molecular liquid crystal, so that the long axis of the molecule of the (A) photoreactive polymer liquid crystal is in the liquid crystal cell, the When disposing in a desired state, (B) the low-molecular-weight liquid crystal can also be disposed in a desired state in the liquid crystal cell. That is, when (A) the photoreaction of the photoreactive polymer liquid crystal is to be fully generated, the direction of the incident light of the polarized ultraviolet light and the direction of the long axis of the molecule of the (A) photoreactive polymer liquid crystal are made to be close to vertical, and the process is carried out. Exposure to polarized UV light is sufficient.

For example, when the polarized ultraviolet light is exposed in the normal direction of the liquid crystal cell, the molecular long axes of both (A) the photoreactive polymer liquid crystal and (B) the low molecular weight liquid crystal in the photoreactive composition are The substrate surface may be arranged in a horizontal direction, and the material of the film included in the substrate is not limited as long as it is such a film.

In addition, (A) when the molecular long axis of the photoreactive polymer liquid crystal is not horizontal to the substrate surface, the incident angle of the polarized ultraviolet light may be determined according to the arrangement state of the molecular long axis.

The step [II] is to irradiate the liquid crystal cell obtained in [I] with polarized ultraviolet light line steps. The polarized ultraviolet rays are irradiated from the outside of either of the two transparent substrates, so the transparent substrate system is as above, and the polarized ultraviolet rays are transmitted through the substrate.

The polarized ultraviolet rays depend on the device to be formed, and ultraviolet rays in the wavelength range of 100 nm to 400 nm can be used. It is preferable to select an optimal wavelength through a filter etc. by the kind of coating film used. In addition, for example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selectively used to selectively initiate a photocrosslinking reaction. As the ultraviolet rays, light emitted from a high-pressure mercury lamp can be used, for example.

When polarized ultraviolet rays are irradiated, the following mechanism occurs in the liquid crystal cell. That is, the (A) photoreactive polymer liquid crystal in the liquid crystal cell has an alignment that matches the polarized ultraviolet rays.

In addition, the (B) low-molecular-weight liquid crystal is aligned according to the alignment of the (A) photoreactive polymer liquid crystal.

Thereby, (A) photoreactive polymer liquid crystal and (B) low molecular weight liquid crystal combine with polarized ultraviolet rays, and become those having alignment.

In addition, only by exposure to polarized ultraviolet rays, as described above, it is possible to have alignment, but it is insufficient. In addition, it is necessary to have the step of [III] heating the liquid crystal cell, specifically, heating the liquid crystal cell to a higher level than the above-mentioned (A) light. A step in which the lower limit of the temperature range in which the reactive polymer liquid crystal exhibits liquid crystallinity is 50°C lower than the temperature. At this time, heating may be performed together with exposure to polarized ultraviolet rays, and/or after exposure to polarized ultraviolet rays, heating may be performed.

Here, the heating may be performed at a temperature ((Tx-50)°C) 50°C lower than the lower limit value (Tx) of the temperature range in which the (A) photoreactive polymer liquid crystal exhibits liquid crystallinity ((Tx-50)°C) or more The high temperature is preferably 65 to 150°C, more preferably 70 to 120°C.

For example, i) exposing the liquid crystal cell with polarized ultraviolet rays; ii) exposing the liquid crystal cell in the state of heating the liquid crystal cell in the above temperature range; iii) after exposing the above i), heating in the above temperature range; Or iv) after the above ii), heating in the above temperature range; (A) the photoreactive polymer liquid crystal has alignment, and thereby the (B) low molecular liquid crystal also has alignment. By using such a procedure, (B) a light-adjusting element in which the low-molecular-weight liquid crystal is uniaxially aligned can be produced.

Moreover, in this case, "dimming element" refers to the liquid crystal whose alignment is controlled to be driven by an applied voltage to control the transmission of light from the back. Non-transmissive elements also include displays (display elements) or window dimming films (glass).

[Example]

(Example 1)

After adding 5 parts by weight of the photoreactive polymer liquid crystal represented by the following formula P6CB to 95 parts by weight of the low molecular weight liquid crystal (E7) produced by Merck Co., Ltd. represented by the following formula E7, it was stirred at 180° C. for 20 minutes to obtain a photoreaction Liquid crystal composition.

Then, liquid crystal cell A1 was produced by encapsulating the photoreactive liquid crystal composition in parallel flat unit cells with a pitch of 2 μm composed of a glass substrate provided with ITO on both sides of the substrate.

The obtained liquid crystal cell A1 was heated to 80° C., and exposed to polarized ultraviolet rays to form a liquid crystal cell B1 in which the alignment of the liquid crystal was controlled.

In addition, the photoreactive polymer liquid crystal system represented by the formula P6CB exhibits liquid crystallinity at 115° C. or higher.

Specifically, using a uniform exposure apparatus (KIN-ITSU-KUN (manufactured by Yamashita Denso Co., Ltd.)) as shown in FIG. 1 , linearly polarized light with a wavelength of 313 nm (22 mW/cm ² ) was used to obtain an exposure amount of 2 J/cm ² state, exposure is performed from the normal direction of the liquid crystal cell A1. The temperature during exposure was controlled using a temperature controller manufactured by INSTEC. Further, the uniform exposure apparatus 1 of FIG. 1 includes an ultraviolet light emitting portion 2 for uniformly emitting ultraviolet rays over the entire light emitting surface, a polarizer 3 disposed below the light emitting portion, and a sample stage 5 on which a sample 4 is placed under the light emitting portion. . The temperature control unit 6 can be disposed between the sample 4 and the sample stage 5 via the temperature control unit 6 to heat the sample during exposure and/or to heat the sample after exposure.

<Alignment state of low molecular liquid crystal>

After the liquid crystal cell B1 is produced, in order to confirm the alignment state of the low-molecular-weight liquid crystal, in the experimental system shown in FIG. 2 , the transmitted light intensity when the liquid crystal cell is rotated is measured. In addition, the alignment state of the low-molecular-weight liquid crystal can also be confirmed by a polarizing microscope.

The measurement results by the experiment shown in FIG. 2 are shown in FIG. 3 , and the observation results by the polarizing microscope are shown in Table 1 respectively.

In addition, the experimental system 11 in FIG. 2 is composed of a He-Ne laser 12, a polarizer 13, an analyzer 14 and a power meter 15, and the polarizer 13, the analyzer 15 are used The order of the device 14 and the power meter 15 is arranged to receive the laser irradiated by the He-Ne laser 12 . In addition, the polarizer 13 and the analyzer 14 are arranged in a state of cross polarization. The sample 16 is disposed between the polarizer 13 and the analyzer 14 , and the transmitted light intensity when the sample 16 is rotated is detected by the power meter 15 .

From FIG. 3 , the following situation can be understood. That is, when the optical axis of the liquid crystal cell is tilted by 45 degrees with respect to the polarizer and the analyzer, the maximum transmitted light intensity is displayed. Therefore, it can be seen that the liquid crystal in the liquid crystal cell is controlled to be uniaxially aligned. This shows that the liquid crystal in the liquid crystal cell exhibits one-axis alignment.

In addition, as can be seen from Table 1, the liquid crystal in the liquid crystal cell is uniaxially aligned by the observation result of the polarizing microscope.

In addition, it was also confirmed that when a voltage was applied to the liquid crystal cell B1, the liquid crystal in the cell was driven according to the magnitude of the applied voltage, and it was confirmed that the liquid crystal cell B1 could act as a dimming element.

(Example 2)

In the same manner as in Example 1, liquid crystal cell A1 was produced. The liquid crystal cell A1 was exposed to polarized ultraviolet rays at room temperature, and then heated at 80° C. for 30 minutes to form a liquid crystal cell B2 in which the alignment of the liquid crystal was controlled.

The obtained liquid crystal cell B2 was the same as that of Example 1, and the alignment state of the low-molecular-weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope (Table 1).

The measurement results of the liquid crystal cell B2 by the experiment shown in FIG. 2 are shown in FIG. 4 . It can be known from FIG. 4 that the liquid crystal in the liquid crystal cell B2 is uniaxially aligned. In addition, it was also found by observation with a polarizing microscope that the liquid crystal in the liquid crystal cell B2 was uniaxially aligned (Table 1, FIG. 4 ).

In addition, the driving of the liquid crystal can also be confirmed by applying a voltage, and it is confirmed that the liquid crystal cell B2 can act as a dimming element.

(Comparative Example 1)

A liquid crystal cell CE1 was produced in the same manner as in Example 1, except that the liquid crystal composition encapsulated in the parallel plate unit cell was only E7, and the liquid crystal cell CE1 was subjected to polarized light exposure in the same manner as in Example 1, and the transmitted light intensity was measured. This result, even if the Furthermore, the temperature dependence of the transmitted light intensity was not observed in the heating temperature performed together with the polarized light exposure. In addition, the alignment of the liquid crystal could not be confirmed as a result of observation with a polarizing microscope.

(Comparative Example 2)

In the same manner as in Example 1, liquid crystal cell A1 was produced. The liquid crystal cell A1 was subjected to polarized ultraviolet light exposure in a state of being heated at 30° C. to form a liquid crystal cell CE2.

The obtained liquid crystal cell CE2 was the same as that of Example 1, and the alignment state of the low-molecular-weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope (Table 1, FIG. 3 ). As a result, the angular dependence of the transmitted light intensity was small, and a sufficient axial alignment of the liquid crystal could not be confirmed. In addition, as a result of observation with a polarizing microscope, the alignment of the liquid crystal was also insufficient.

(Comparative Example 3)

In the same manner as in Example 1, liquid crystal cell A1 was produced. The liquid crystal cell A1 is subjected to polarized ultraviolet light exposure in a state of being heated at 50° C. to form a liquid crystal cell CE3.

The obtained liquid crystal cell CE3 was the same as that of Example 1, and the alignment state of the low-molecular-weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope (Table 1, FIG. 3 ). As a result, the angular dependence of the transmitted light intensity was small, and a sufficient axial alignment of the liquid crystal could not be confirmed. In addition, as a result of observation with a polarizing microscope, the alignment of the liquid crystal was also insufficient.

(Comparative Example 4)

Liquid crystal cell A1 was produced in the same manner as in Example 1. The liquid crystal cell A1 was exposed to polarized ultraviolet rays at room temperature, and then the liquid crystal cell was heated at 30° C. for 30 minutes to form the liquid crystal cell CE4.

The obtained liquid crystal cell CE4 was the same as that of Example 1, and the alignment state of the low-molecular-weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope (Table 1, FIG. 4 ). As a result, the angular dependence of the transmitted light intensity was small, and a sufficient axial alignment of the liquid crystal could not be confirmed. In addition, as a result of observation with a polarizing microscope, the alignment of the liquid crystal was also insufficient.

(Comparative Example 5)

Liquid crystal cell A1 was produced in the same manner as in Example 1. The liquid crystal cell A1 was exposed to polarized ultraviolet rays at room temperature, and then the liquid crystal cell was heated at 50° C. for 30 minutes to form the liquid crystal cell CE5.

The obtained liquid crystal cell CE5 was the same as that of Example 1, and the alignment state of the low-molecular-weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope (Table 1, FIG. 4 ). As a result, the angular dependence of the transmitted light intensity was small, and a sufficient axial alignment of the liquid crystal could not be confirmed. In addition, as a result of observation with a polarizing microscope, the alignment of the liquid crystal was also insufficient.

It is known from Examples 1, 2 and Comparative Example 1 that the liquid crystal composition of the present invention has (A) photoreactive polymer liquid crystal; and (B) low molecular liquid crystal; the liquid crystal composition of Examples 1 and 2 However, the liquid crystal composition of Comparative Example 1 did not show photoreactivity. In addition, by using the liquid crystal composition of Example 1, it was found that a liquid crystal with a one-axis alignment of the liquid crystal could be produced. unit cell. In addition, when Examples 1 and 2 were compared with Comparative Examples 2 to 5, it was found that because of having a specific heating step, a liquid crystal cell in which the liquid crystal was uniaxially oriented could be produced.

Claims (3)

A photoreactive liquid crystal composition comprising (A) a photoreactive polymer liquid crystal represented by the following formula P6CB; and (B) a low molecular weight liquid crystal represented by the following formula E7; a photoreactive liquid crystal composition, The weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) low molecular weight liquid crystal) is 3:97~20:80

A light-adjusting element formed by having a liquid crystal cell containing the photoreactive liquid crystal composition as claimed in claim 1. A dimming element comprising a liquid crystal cell containing the photoreactive liquid crystal composition as claimed in claim 1, wherein (B) the low molecular liquid crystal has a specific orientation in the liquid crystal cell.

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