CN105393167A - Method for producing substrate having liquid crystal orientation film for in-plane-switching liquid-crystal display element - Google Patents

Abstract

The present invention provides an in-plane-switching liquid-crystal display element having superior burn-in properties and to which an orientation control ability has been imparted at a high efficiency. The present invention achieves same by means of a method that is for producing a substrate having a liquid crystal orientation film for an in-plane-switching liquid-crystal display element to which an orientation control ability has been imparted and that obtains the liquid crystal orientation film by means of having: [I] a step for forming a coating film by applying onto a substrate having a conductive film for in-plane switching a polymer composition containing (A) a photosensitive side-chain polymer exhibiting liquid crystal properties in a predetermined temperature range and (B) an organic solvent; [II] a step for radiating polarized ultraviolet rays at the coating film obtained in [I]; [III] a step for heating the coating film obtained in [II]; and [IV] a step for cooling the coating film heated in [III] to a temperature less than the glass transition temperature of the surface of the coating film, and then re-heating to a temperature that is at least the glass transition temperature.

Description

Manufacturing method of substrate having liquid crystal alignment film for lateral electric field driven type liquid crystal display element

technical field

The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element. More specifically, it relates to a new method for producing a liquid crystal display element excellent in image sticking characteristics.

Background technique

Liquid crystal display devices are known as display devices that are light in weight, thin in cross-section, and low in power consumption. In recent years, they have been used in large-scale television applications, etc., and have achieved remarkable development. The liquid crystal display element is constituted, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. Also, in a liquid crystal display element, an organic film containing an organic material is used as a liquid crystal alignment film to make liquid crystals exhibit a desired alignment state between substrates.

That is, the liquid crystal aligning film is a constituent part of the liquid crystal display element, and is formed on the surfaces of the substrates sandwiching the liquid crystal that are in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a specific direction between the substrates. Furthermore, in addition to the function of orienting the liquid crystal in a specific direction such as a direction parallel to the substrate, the liquid crystal aligning film may also require the function of controlling the pretilt angle of the liquid crystal. The ability (henceforth orientation control ability) of such a liquid crystal aligning film to control the liquid crystal orientation is provided by performing an orientation process to the organic film which comprises a liquid crystal aligning film.

Conventionally, a brush rubbing method is known as an orientation treatment method for a liquid crystal aligning film for providing an orientation control ability. The brushing method refers to a method of rubbing (brushing) the surface of an organic film such as polyvinyl alcohol, polyamide, polyimide, etc. on a substrate in a constant direction with a cloth such as cotton, nylon, or polyester. , so that the liquid crystal is aligned along the rubbing direction (brushing direction). This brushing method can easily realize a relatively stable liquid crystal alignment state, so it is used in the conventional manufacturing process of liquid crystal display elements. Moreover, as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and electric characteristic is mainly selected.

However, the rubbing method of rubbing the surface of the liquid crystal aligning film containing polyimide etc. has the problem of dust generation and static electricity generation. In addition, due to the high-definition of liquid crystal display elements in recent years, the unevenness caused by the electrodes on the corresponding substrate or the switching active elements for liquid crystal driving, it is impossible to rub the surface of the liquid crystal alignment film uniformly with a cloth, and it is impossible to achieve a uniform liquid crystal. orientation.

Therefore, as another orientation treatment method of the liquid crystal aligning film which does not perform brush rubbing, the photo-alignment method is actively studied.

There are various photo-alignment methods. Linearly polarized light or collimated light forms anisotropy in an organic film constituting a liquid crystal alignment film, and aligns liquid crystals based on the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. In this method, for example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition occurs by utilizing the polarization direction dependence of ultraviolet absorption of the molecular structure. And the liquid crystal is aligned by the polyimide which remained without decomposing (for example, refer patent document 1).

In addition, photo-crosslinking-type and photo-isomerization-type photo-alignment methods are also known as other photo-alignment methods. In the photo-crosslinking type photo-alignment method, for example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) of double bond portions of two side chains parallel to the polarized light. And, the liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In the photoisomerization-type photo-alignment method, when using a side chain-type polymer having azobenzene in the side chain, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene moiety parallel to the side chain of the polarized light. , aligning the liquid crystal in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, in the method of aligning the liquid crystal aligning film by the photo-alignment method, there is no need to perform brushing, and there is no need to worry about dust and static electricity. In addition, alignment treatment can be performed even on a substrate of a liquid crystal display element having irregularities on the surface, thus becoming an alignment treatment method for a liquid crystal alignment film suitable for an industrial production process.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3893659

non-patent literature

Non-Patent Document 1: M. Shadte et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

Non-Patent Document 2: K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

Contents of the invention

The problem to be solved by the invention

As described above, compared with the brushing method that has been used industrially as an alignment treatment method for liquid crystal display elements, the photo-alignment method has a significant advantage because it does not require a brushing step. In addition, compared with the brushing method in which the orientation control ability by brushing is basically fixed, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, when the photo-alignment method is intended to achieve the same degree of alignment control ability as that achieved by the brush rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be achieved.

For example, in the decomposition-type photo-alignment method described in the above-mentioned Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light emitted from a high-pressure mercury lamp with a power of 500 W for 60 minutes, and a long time and a large amount of ultraviolet irradiation are required. In addition, in the case of a dimerization type or a photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Furthermore, in the case of photo-crosslinking type and photo-isomerization type photo-alignment methods, the thermal stability and photostability of liquid crystal alignment are poor, so when it is made into a liquid crystal display element, there are concerns about poor alignment and image sticking. In particular, in a transverse electric field driven liquid crystal display device, liquid crystal molecules are switched in-plane, and therefore liquid crystal alignment shift after liquid crystal driving and display sticking by AC driving are obvious problems.

Therefore, in the photo-alignment method, high efficiency of the alignment treatment and stable liquid crystal alignment are required, and a liquid crystal aligning film, a liquid crystal aligning agent, and an alignment method capable of efficiently imparting high alignment control ability to the liquid crystal aligning film are required.

An object of the present invention is to provide a substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element, which is endowed with orientation control ability with high efficiency and excellent in image sticking characteristics, and a lateral electric field driven liquid crystal display element having the substrate. Another object of this invention is to provide the manufacturing method of the board|substrate with a liquid crystal aligning film which can expand the boundary range of the irradiation amount of the polarized ultraviolet-ray which can realize the favorable liquid crystal orientation in a liquid crystal aligning film.

solutions to problems

The inventors of the present invention conducted intensive studies to achieve the above-mentioned problems, and as a result, found the following invention.

<1> a kind of manufacture method that has the substrate of transverse electric field drive type liquid crystal display element liquid crystal aligning film, it obtains the aforementioned liquid crystal aligning film that has been endowed orientation control ability by possessing following procedure:

[I] A process of coating a polymer composition on a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition containing: (A) exhibiting liquid crystallinity in a specific temperature range Photosensitive side chain polymer, and (B) organic solvent;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I];

[III] A step of heating the coating film obtained in [II]; and

[IV] A step of cooling the coating film heated in [III] to a temperature lower than the glass transition temperature of the coating film surface, and then heating to a temperature higher than the glass transition temperature.

<2> In the above <1>, the cooling temperature of the coating film in the step [IV] may be 10° C. or more lower than the glass transition point temperature (Tg) of the side chain type polymer as the component (A).

<3> In the above <1> or <2>, the heating temperature of the coating film after ultraviolet irradiation and the reheating temperature after cooling may be higher than the glass transition temperature of the coating film surface and less than the homogeneous phase transition of the coating film surface temperature temperature.

<4> In any one of <1> to <3> above, the (A) component may have a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofries rearrangement.

<5> In any one of said <1>-<4>, (A) component may have any one photosensitive side chain selected from the group which consists 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 atoms bonded to them are optionally substituted by halogen groups;

T is a single bond or an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

Y represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings through the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 2 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen substitution;

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons. 5's alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

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 reaches 2, X is optionally the same or different from each other;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkoxy group with 1 to 5 carbons;

One of q1 and q2 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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof; Among them, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more When , P is optionally the same or different from each other, and when the number of Q reaches 2 or more, Q is optionally the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;

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

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

<6> In any one of said <1>-<4>, (A) component may have any one photosensitive side chain selected from the group which consists of following formula (7)-(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, m1 and m2 represent an integer from 1 to 3;

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

<7> In any one of said <1>-<4>, (A) component may have any one photosensitive side chain selected from the group which consists of following formula (11)-(13).

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

<8> In any one of said <1>-<4>, (A) component may have the photosensitive side chain represented by following formula (14) or (15).

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

<9> In any one of said <1>-<4>, (A) component may have the photosensitive side chain represented by following formula (16) or (17).

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

<10> In any one of said <1>-<4>, (A) component may have the photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen.

<11> In any one of said <1>-<4>, (A) component may have the photosensitive side chain represented by following formula (20).

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

<12> In any one of <1> to <11> above, the component (A) may have any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

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

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons, or alkoxy groups with 1 to 12 carbons;

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

R ₂ represents a hydrogen atom, -NO2, -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbons and alkanes with 5 to 8 carbons group or alkoxy group;

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

<13> The board|substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by any one of said <1>-<12>.

<14> A lateral electric field driven liquid crystal display element comprising the substrate of the above <13>.

<15> A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by having the following steps:

A step of preparing the substrate (first substrate) of <13> above;

A step of obtaining a second substrate having a liquid crystal aligning film that is provided with the following steps [I'], [II'], and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and

[V] The process of arranging the first substrate and the second substrate facing each other in such a way that the liquid crystal alignment films of the first substrate and the second substrate face each other through the liquid crystal, thereby obtaining a liquid crystal display element,

Described operation [I '], [II '] and [III '] are:

[I'] A step of forming a coating film by coating a polymer composition containing: (A) a photosensitive side chain-type polymer exhibiting liquid crystallinity in a specific temperature range; molecule, and (B) an organic solvent;

[II'] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and

[III'] A step of heating the coating film obtained in [II'].

<16> In the above <15>, the step of obtaining the aforementioned second substrate may include [IV'] cooling the coating film heated in [III'] to a temperature lower than the glass transition temperature of the coating film surface, and then A step of heating to a temperature equal to or higher than the glass transition temperature.

<17> A lateral electric field driven liquid crystal display element manufactured by the above-mentioned <15> or <16>.

Moreover, the following invention was found as another aspect.

<P1> A method of manufacturing a substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element, comprising the following steps to obtain the liquid crystal alignment film endowed with orientation control capability

[I] A process of coating a polymer composition on a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition containing: (A) exhibiting liquid crystallinity in a specific temperature range Photosensitive side chain polymer, and (B) organic solvent;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I];

[III] A step of heating the coating film obtained in [II]; and

[IV] A step of cooling the coating film heated in [III] to a temperature lower than the glass transition temperature of the coating film surface, and then heating to a temperature higher than the glass transition temperature.

<P2> In the above <P1>, the cooling temperature of the coating film in the step [IV] may be a temperature lower than the glass transition point temperature (Tg) of the side chain polymer as the component (A) by 10° C. or more.

<P3> In the above <P1> or <P2>, the heating temperature of the coating film after ultraviolet irradiation and the reheating temperature after cooling may be higher than the glass transition temperature of the coating film surface and less than the homogeneous phase transition of the coating film surface temperature temperature.

<P4> In any one of <P1> to <P3> above, the (A) component may have a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofries rearrangement.

<P5> In any one of <P1> to <P4> above, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (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 atoms bonded to them are optionally substituted by halogen groups;

T is a single bond or an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

Y represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings through the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 2 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen substitution;

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons. 5's alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- ;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkoxy group with 1 to 5 carbons;

One of q1 and q2 is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently selected from the group consisting of a single bond, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with 5 to 8 carbon atoms, and combinations thereof group. Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded to is an aromatic ring;

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

<P6> In any one of <P1> to <P4> above, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (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, m1 and m2 represent an integer from 1 to 3;

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

<P7> In any one of said <P1>-<P4>, (A) component may have any one photosensitive side chain selected from the group which consists of following formula (11)-(13).

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

<P8> In any one of said <P1>-<P4>, (A) component may have the photosensitive side chain represented by following formula (14) or (15).

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

<P9> In any one of said <P1>-<P4>, (A) component may have the photosensitive side chain represented by following formula (16) or (17).

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

<P10> In any one of said <P1>-<P4>, (A) component may have the photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen.

<P11> In any one of said <P1>-<P4>, (A) component may have the photosensitive side chain represented by following formula (20).

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

<P12> In any one of <P1> to <P11> above, the component (A) may have any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

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

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons, or alkoxy groups with 1 to 12 carbons;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein, in formulas (25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), all m The sum of is 1 or more, and m1, m2 and m3 each independently represent an integer of 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 heterocycle, and an alicyclic hydrocarbon with 5 to 8 carbons and Alkyl or alkoxy;

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

<P13> A substrate having a liquid crystal aligning film for a lateral electric field drive type liquid crystal display element, manufactured by any one of <P1> to <P12>.

<P14> A lateral electric field driven liquid crystal display element having the substrate of the above-mentioned <P13>.

<P15> A method for manufacturing a transverse electric field driven liquid crystal display element, which obtains the liquid crystal display element by having the following steps:

The process of preparing the substrate (first substrate) of <P13> above;

A step of obtaining a second substrate having a liquid crystal aligning film that is provided with the following steps [I'], [II'], and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and

[V] a process of arranging the first substrate and the second substrate facing each other in such a way that the liquid crystal alignment films of the first substrate and the second substrate face each other through the liquid crystal, thereby obtaining a liquid crystal display element;

Described operation [I '], [II '] and [III '] are:

[I'] A step of forming a coating film by coating a polymer composition containing: (A) a photosensitive side chain-type polymer exhibiting liquid crystallinity in a specific temperature range; molecule, and (B) an organic solvent;

[II'] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and

[III'] A step of heating the coating film obtained in [II'].

<P16>In <P15> above,

The step of obtaining the aforementioned second substrate may include [IV'] cooling the coating film heated in [III'] to a temperature lower than the glass transition temperature of the surface of the coating film, and then heating to a temperature above the glass transition temperature. temperature process.

<P17> A lateral electric field driven liquid crystal display element manufactured by the above <P15> or <P16>.

The effect of the invention

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element, which is provided with orientation control ability at high efficiency and excellent in image sticking characteristics, and a lateral electric field driven liquid crystal display element having the substrate.

The lateral electric field driven liquid crystal display element produced by the method of the present invention is efficiently endowed with orientation control capability, and therefore does not impair display characteristics even if it is driven continuously for a long time.

In addition, according to the present invention, the boundary range of the polarized light irradiation amount capable of achieving good liquid crystal orientation in the liquid crystal alignment film can be expanded, and since the boundary range of the irradiation amount is expanded, the desired effect can be achieved in a wider irradiation range .

Description of drawings

Fig. 1 is a diagram schematically illustrating an example of the anisotropy introducing treatment in the manufacturing method of the liquid crystal aligning film used in the present invention, and the photosensitive side chain uses a crosslinkable organic group and introduces anisotropy hour graph.

Fig. 2 is a diagram schematically illustrating an example of anisotropy introducing treatment in a method for producing a liquid crystal alignment film used in the present invention, and is an anisotropy introduced by using a crosslinkable organic group as a photosensitive side chain. big picture.

Fig. 3 is a diagram schematically illustrating an example of anisotropy introducing treatment in the method for producing a liquid crystal alignment film used in the present invention, and the photosensitive side chain uses an organic compound that undergoes Fries rearrangement or isomerization. group and the graph of the introduced anisotropy hours.

4 is a diagram schematically illustrating an example of the anisotropy introducing treatment in the method for producing a liquid crystal alignment film used in the present invention, and the photosensitive side chain uses an organic compound that undergoes Fries rearrangement or isomerization. group and the introduced anisotropy is large.

detailed description

As a result of intensive studies, the inventors of the present invention obtained the following knowledge and completed the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer (hereinafter also simply referred to as a side chain type polymer) capable of exhibiting liquid crystallinity, and the coating film obtained by using the above polymer composition has A film of a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. The coating film does not need to be brushed, but is oriented by polarized light irradiation. And after polarized light irradiation, it becomes the coating film (henceforth a liquid crystal aligning film) provided with orientation control ability through the process of heating this side chain type polymer film. At this time, the minute anisotropy expressed by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is efficiently reoriented by self-assembly. As a result, efficient orientation process can be realizable as a liquid crystal aligning film, and the liquid crystal aligning film provided with high orientation control ability can be obtained.

The inventors of the present invention also unexpectedly found that after irradiating polarized light, the product obtained by heating the side chain type polymer film is further cooled and reheated to obtain a coating film endowed with orientation control ability, thereby obtaining A liquid crystal aligning film with good liquid crystal orientation in a wider boundary range of polarized light irradiation. The present invention has been made based on these findings.

Hereinafter, embodiments of the present invention will be described in detail.

<Manufacturing Method of Substrate Having Liquid Crystal Alignment Film> and <Manufacturing Method of Liquid Crystal Display Element>

The manufacturing method of the substrate with liquid crystal alignment film of the present invention has following steps:

[I] A process of coating a polymer composition on a substrate having a conductive film for driving a transverse electric field to form a coating film, the polymer composition containing: (A) exhibiting liquid crystallinity in a specific temperature range Photosensitive side chain polymer, and (B) organic solvent;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I];

[III] A step of heating the coating film obtained in [II]; and

[IV] A step of cooling the coating film heated in [III] to a temperature lower than the glass transition temperature of the coating film surface, and then heating to a temperature higher than the glass transition temperature.

Through the said process, the liquid crystal aligning film for lateral electric field drive type liquid crystal display elements provided with orientation control ability can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

In addition, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a transverse electric field drive type liquid crystal display element can be obtained.

In addition to using a substrate without a transverse electric field driving conductive film instead of a substrate with a transverse electric field driving conductive film, the second substrate is obtained by using the above-mentioned steps [I] to [III] (due to using a conductive film without a transverse electric field driving The substrate of the film, therefore, may be simply referred to as steps [I'] to [III'] in this application for convenience), and a second substrate having a liquid crystal aligning film endowed with orientation control ability can be obtained.

The manufacturing method of the lateral electric field driven liquid crystal display element has the following steps:

[V] A step of arranging the first substrate and the second substrate obtained above so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween, to obtain a liquid crystal display element. Thereby, a transverse electric field drive type liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [IV] and [V] included in the production method of the present invention will be described.

<Process[I]>

In step [I], a polymer composition is coated on a substrate having a conductive film for driving a transverse electric field to form a coating film. The polymer composition contains: a photosensitive side that exhibits liquid crystallinity in a specific temperature range chain polymers, and organic solvents.

<substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a highly transparent substrate. In this case, it is not particularly limited, and plastic substrates such as glass substrates, acrylic substrates, and polycarbonate substrates can be used.

In addition, in consideration of application to reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used.

<Conductive film for lateral electric field drive>

The substrate has a conductive film for lateral electric field driving.

As this conductive film, when a liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide: indium tin oxide), IZO (Indium Zinc Oxide: indium zinc oxide) etc. are mentioned, It is not limited to these.

In addition, in the case of a reflection type liquid crystal display element, as a conductive film, the material which reflects light, such as aluminum, etc. are mentioned, It is not limited to these.

As a method of forming a conductive film on a substrate, conventionally known methods can be used.

<Polymer composition>

Coating a polymer composition on a substrate having a conductive film for driving a transverse electric field, especially coating a polymer composition on a conductive film.

The polymer composition used in the production method of the present invention contains: (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a specific temperature range; and (B) an organic solvent.

<<(A) Side chain polymer>>

(A) The component is a photosensitive side chain type polymer which expresses liquid crystallinity in a specific temperature range.

(A) The side chain type polymer may react with light in the wavelength range of 250 nm to 400 nm and exhibit liquid crystallinity in the temperature range of 100°C to 300°C.

(A) The side chain type polymer preferably has a photosensitive side chain that reacts with light in a wavelength range of 250 nm to 400 nm.

(A) Since the side chain type polymer exhibits liquid crystallinity in the temperature range of 100°C to 300°C, it preferably has a mesogen group.

(A) A photosensitive side chain is bonded to the main chain of the side chain type polymer, and can undergo crosslinking reaction, isomerization reaction, or photofries rearrangement in response to light. The photosensitive side chain structure is not particularly limited, but is preferably a structure that undergoes a crosslinking reaction or photo-Friesian rearrangement in response to light, more preferably a structure that undergoes a crosslinking reaction. In this case, even when exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer film capable of expressing liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. At this time, when this side chain type polymer is used as a liquid crystal aligning film, stable liquid crystal orientation can be obtained.

The structure of this polymer can be made into the following structure, for example: it has a main chain and a side chain bonded thereto, and the side chain has a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene Mesogen components such as mesogen groups and photosensitive groups that are bonded to the front end to induce crosslinking reactions and isomerization reactions; have a main chain and a side chain bonded to it, and the side chain has both Components also undergo a photofries rearrangement of the phenylbenzoate group.

As a more specific example of the structure of a photosensitive side chain type polymer film capable of exhibiting liquid crystallinity, it is preferably a structure having a main chain and a side chain consisting of a compound selected from hydrocarbons and (meth)acrylates. , itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other free radical polymerizable groups and at least one of the group consisting of siloxane, and the side chain contains at least one of the following formulas (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 atoms bonded to them are optionally substituted by halogen groups;

T is a single bond or an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them are optionally substituted by halogen groups;

Y represents _a ring selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons with 5 to 8 carbon atoms, or the same or different substituents selected from these substituents The group formed by bonding 2 to 6 rings through the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or a carbon number of 1 to 2 5 alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen substitution;

_Y2 is a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and is bonded to them The hydrogen atoms in are independently optionally replaced by -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons. 5's alkoxy substitution;

R represents a hydroxyl group, an alkoxy group with 1 to 6 carbons, or the same definition as _Y1 ;

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 reaches 2, X is optionally the same or different from each other;

Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are each independently optionally replaced by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH= Substituted by CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkoxy group with 1 to 5 carbons;

One of q1 and q2 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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons with 5 to 8 carbon atoms, and combinations thereof; Among them, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more When , P is optionally the same or different from each other, and when the number of Q reaches 2 or more, Q is optionally the same or different from each other;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

When both l1 and l2 are 0, when T is a single bond, A also represents a single bond;

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

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

The side chain may be any photosensitive side chain selected from the group consisting of the following formulas (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, m1 and m2 represent an integer from 1 to 3;

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

The side chain may be any photosensitive side chain selected from the group consisting of the following formulas (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 photosensitive 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 photosensitive side chain represented by the following formula (16) or (17).

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

In addition, the side chain may be a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkane with 1 to 5 carbons Oxygen.

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

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

In addition, the (A) side chain type polymer may have any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

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

_Y3 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 heterocycle, and an alicyclic hydrocarbon with a carbon number of 5 to 8, and combinations thereof, the bond The hydrogen atoms associated with them are each independently optionally substituted by -NO ₂ , -CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkoxy group with 1 to 5 carbons;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a Azacyclic rings, alicyclic hydrocarbons with 5 to 8 carbons, alkyl groups with 1 to 12 carbons, or alkoxy groups with 1 to 12 carbons;

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

R ₂ represents a hydrogen atom, -NO2, -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbons and alkanes with 5 to 8 carbons group or alkoxy group;

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

<<Preparation method of photosensitive side chain type polymer>>

The above-mentioned photosensitive side chain type polymer capable of expressing liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the above-mentioned photosensitive side chain and a liquid crystalline side chain monomer.

[Photoreactive Side Chain Monomer]

The photoreactive side chain monomer means a monomer capable of forming a polymer having a photosensitive side chain at a side chain site of the polymer when forming a polymer.

As a photoreactive group which a side chain has, the following structures and derivatives thereof are preferable.

As a more specific example of a photoreactive side chain monomer, it is preferably a structure having a polymerizable group and a photosensitive side chain, and the polymerizable group is selected from hydrocarbons, (meth)acrylates, and itaconate esters. , fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other free radical polymerizable groups and siloxane The photosensitive side chain is a photosensitive side chain comprising at least one of the above formulas (1) to (6), preferably, for example, comprising the above formulas (7) to (10) A photosensitive side chain of at least one of the above, a photosensitive side chain containing at least one of the above formulas (11) to (13), a photosensitive side chain represented by the above formula (14) or (15), the above The photosensitive side chain represented by formula (16) or (17), the photosensitive side chain represented by said formula (18) or (19), and the photosensitive side chain represented by said formula (20).

In the present application, novel compounds (1) to (11) represented by the following formulas (1) to (11) are provided as photoreactive and/or liquid crystalline side chain monomers; and the following formulas (12) to Compounds (12) to (17) represented by (17).

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group with 2 to 10 carbons; R10 represents Br or CN; S represents an alkylene group with 2 to 10 carbons; u represents 0 or 1; and Py represents 2-pyridyl, 3-pyridyl or 4-pyridyl. Also, v represents 1 or 2.

[Liquid crystal side chain monomer]

The liquid crystalline side chain monomer refers to a monomer in which a polymer derived from the monomer exhibits liquid crystallinity, and the polymer can form a mesogen group at a side chain site.

The mesogen group in the side chain may be a group that forms a mesogen structure alone such as biphenyl or phenyl benzoate, or a group that forms a mesogen structure through hydrogen bonding between side chains such as benzoic acid. group. As a mesogen group which a side chain has, it is preferable to have the following structure.

As a more specific example of a liquid crystal side chain monomer, it is preferably a structure having a polymerizable group selected from hydrocarbons, (meth)acrylates, itaconate esters, and side chains as follows: Fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other free radical polymerizable groups and siloxane At least one of the above-mentioned side chains comprises at least one of the above-mentioned formulas (21) to (31).

(A) The side chain type polymer can be obtained by the polymerization reaction of the photoreactive side chain monomer which expresses liquid crystallinity mentioned above. In addition, it can be obtained by copolymerization of a photoreactive side chain monomer not expressing liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer expressing liquid crystallinity and a liquid crystalline side chain monomer. Furthermore, it can be copolymerized with other monomers within the range which does not impair the ability to express liquid crystallinity.

Examples of other monomers include industrially available monomers capable of radical polymerization.

Specific examples of other monomers include 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.

Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenylmethyl acrylate, phenyl acrylate, acrylic acid 2,2,2 - Trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, acrylic acid Tetrahydrofurfuryl, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricycloacrylate Decyl ester, and 8-ethyl-8-tricyclodecanyl acrylate, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl Anthracenyl methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2-methoxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, and 8-methacrylic acid -Ethyl-8-tricyclodecanyl ester, etc. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate and (3-ethyl-3-oxetanyl)(meth)acrylate can also be used A (meth)acrylate compound having a cyclic ether group such as cyclobutanyl)methyl ester.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

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

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the side chain type polymer of the present embodiment is not particularly limited, and general industrially applicable methods can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using vinyl groups of liquid crystalline side chain monomers and photoreactive side chain monomers. Among these, radical polymerization is particularly preferable from the viewpoint of easiness of reaction control and the like.

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

The thermal radical polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.) , hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilaurate acyl peroxides, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peroxyesters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, peroxide Oxygenated 2-ethylcyclohexane acid t-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2 '-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used individually by 1 type, or may use it in combination of 2 or more types.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, Isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2- Methyl-4'-isopropyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-keto, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid iso Amyl ester, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(tri Chloromethyl)-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)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl )-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-dichlorobenzene base)-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' -Bimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecyl Carbazole, 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(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-hexylperoxy Carbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxy Carbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-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-benzoyl)ethanone and the like. These compounds may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side-chain type polymer capable of expressing liquid crystallinity is not particularly limited as long as it dissolves the produced polymer. Specific examples thereof are listed below.

Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylamylketone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Ester, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate, 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 mono Methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, three Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl Cyclohexene, 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 monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , Ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropanamide, etc.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve the generated polymer, it can be mixed with the above-mentioned organic solvent and used as long as the generated polymer is not precipitated.

In addition, in the radical polymerization, oxygen in the organic solvent hinders the polymerization reaction, so the organic solvent is preferably used after degassing as much as possible.

The polymerization temperature at the time of radical polymerization can select arbitrary temperature of 30 degreeC - 150 degreeC, Preferably it is the range of 50 degreeC - 100 degreeC. In addition, the reaction can be carried out at any concentration. When the concentration is too low, it is difficult to obtain a high-molecular-weight polymer. When the concentration is too high, the viscosity of the reaction solution becomes too high and it is difficult to stir uniformly. Therefore, the monomer concentration is preferably 1 mass % to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and an organic solvent may be added thereafter.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer becomes smaller. Therefore, the ratio of the radical initiator to the polymerizable monomer is preferably 0.1 mol% to 10 mol%. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of polymers]

When recovering the produced polymer from the reaction solution of the photosensitive side chain type polymer capable of expressing liquid crystallinity obtained by the above reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. . The polymer deposited in the poor solvent and precipitated can be collected by filtration and then dried at normal temperature or under reduced pressure at normal temperature or with heat. In addition, when the operation of redissolving the precipitated polymer in an organic solvent and reprecipitating it is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, and hydrocarbons. When three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

Regarding the molecular weight of the (A) side chain type polymer of the present invention, when considering the strength of the obtained coating film, the workability when forming the coating film, and the uniformity of the coating film, the GPC (GelPermeationChromatography, gel permeation chromatography) method is used. The measured weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared in the form of a coating liquid so as to be suitable for forming a liquid crystal aligning film. That is, the polymer composition used in the present invention is preferably prepared in the form of a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component refers to a resin component containing the above-mentioned photosensitive side chain type polymer capable of expressing liquid crystallinity. In this case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, particularly preferably 3% by mass to 10% by mass.

In the polymer composition of this embodiment, the above-mentioned resin components may all be the above-mentioned photosensitive side-chain polymers capable of exhibiting liquid crystallinity, and may be mixed with other polymers within the range that does not impair liquid crystal expressiveness and photosensitivity. other polymers. In this case, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Examples of such other polymers include poly(meth)acrylates, polyamic acids, polyimides, and the like, and polymers that are not photosensitive side chain-type polymers capable of expressing liquid crystallinity.

<<(B)Organic solvent>>

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples thereof are listed below.

Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N -Vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide , 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone , methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4- Methyl-2-pentanone, propylene glycol monoacetate, 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, 3- Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. They can be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above-mentioned (A) and (B) components. Examples thereof include, but not limited to, solvents or compounds that improve film thickness uniformity and surface smoothness when coating a polymer composition, compounds that improve adhesion between a liquid crystal aligning film and a substrate, and the like.

Specific examples of solvents (poor solvents) that improve film thickness uniformity and surface smoothness include the following solvents.

Examples include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, Butyl Carbitol, Ethyl Carbitol, Ethyl Carbitol Acetate, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl 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, 3-methyl -3-Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyric acid Butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , Ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxypropionate Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl Ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate Solvents with low surface tension such as ester, ethyl lactate, n-propyl lactate, n-butyl lactate, and isopentyl lactate.

These poor solvents may be used individually by 1 type, and may mix and use multiple types. When using the above-mentioned solvent, it is preferably 5% by mass to 80% by mass of the entire solvent, more preferably 20% by mass to 60% by mass, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.

More specifically, for example, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products Corporation); Megafac (registered trademark) F171, F173, R-30 (manufactured by DICCORPORATION); Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited); AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.); Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEI MICHEMICAL CO., LTD.), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the resin component contained in the polymer composition.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the compound etc. which contain the functional silane shown below are mentioned.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureapropyltrimethoxysilane, 3 -Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxy Silylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-trimethoxysilylpropyltriethylenetriamine, Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl -3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl- 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis( Oxyethylene)-3-aminopropyltriethoxysilane, etc.

Furthermore, in order to improve the adhesion between the substrate and the liquid crystal alignment film, and to prevent the decrease in electrical properties caused by the backlight when constituting the liquid crystal display element, the polymer composition may contain the following phenolic plastics, epoxy group-containing compound additives. Specific phenolic plastic additives are shown below, but are not limited to this structure.

Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl base) cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When using a compound for improving the adhesion between the liquid crystal aligning film and the substrate, the amount used is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 100 parts by mass of the resin component contained in the polymer composition. 20 parts by mass. When the usage-amount is less than 0.1 mass parts, the effect which improves adhesiveness cannot be expected, and when it exceeds 30 mass parts, the orientation of a liquid crystal may worsen.

As additives, photosensitizers can also be used. Preferred are leuco sensitizers and triplet sensitizers.

As photosensitizers, there are aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketone coumarin, carbonyl dicoumarin Aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones substituted by amino groups (2-hydroxybenzophenone, single-p-(dimethylamino)-2-hydroxybenzophenone or two-p-(dimethylamino)-2-hydroxybenzophenone amino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3- Methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazole Line, 2-(4-bibenzoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2- (4-bibenzoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxa Azoline (2-benzoylmethylene-3-methyl-β-naphthooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-( α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-bibenzoylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene Methyl)-3-methyl-β-naphthooxazoline, 2-(4-bibenzoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-fluorobenzyl Acylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m-nitroaniline or p-nitroaniline, 2,4,6-trinitroaniline) or Nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthaloketone, acetophenone acetal Ketone (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azo Indolizine, Merlocoumarin, etc.

Preferred are aromatic 2-hydroxyketones (benzophenones), coumarins, coumarinones, carbonyl dicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and benzene Acetone ketal.

In addition to the above-mentioned substances in the polymer composition, as long as it does not impair the effect of the present invention, for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, dielectrics and conductive substances can be added, Furthermore, a crosslinkable compound can be added for the purpose of improving the hardness and density of a film at the time of making it into a liquid crystal aligning film.

The method of coating the above-mentioned polymer composition on the substrate having the conductive film for driving a transverse electric field is not particularly limited.

About the coating method, the method by screen printing, offset printing, flexographic printing, an inkjet method, etc. is common industrially. As other coating methods, there are dipping method, roll coating method, slit coating method, spin coating method (spin coating method), spray coating method, etc., and they can be used according to the purpose.

After coating the polymer composition on a substrate having a conductive film for driving in a transverse electric field, heat it at 50 to 200° C., preferably at 50 to 150° C. The solvent evaporates to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain type polymer.

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness of the coating film is too thin, the reliability of the liquid crystal display element may be reduced, so it is preferably 5nm to 300nm, more preferably 10nm to 10nm. 150nm.

In addition, after the [I] step and before the next [II] step, a step of cooling the substrate on which the coating film is formed to room temperature may be provided.

<Process [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating polarized ultraviolet rays to the film surface of the coating film, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a specific direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select an optimum wavelength by means of a filter or the like according to the kind of coating film to be used. In addition, for example, ultraviolet light with a wavelength in the range of 290nm to 400nm can be selected to induce photocrosslinking reaction selectively. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of exposure to polarized ultraviolet light depends on the coating film to be used. Regarding the irradiation amount, it is preferably within the range of 1% to 70%, more preferably within the range of 1% to 50%, of the amount of polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax). is the difference between the ultraviolet absorbance of the coating film in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.

<Process [III]>

In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. The ability to control orientation can be imparted to the coating film by heating.

For heating, heating means such as a hot plate, a heat circulation type oven, or an IR (infrared ray) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the coating film to be used exhibits liquid crystallinity.

The heating temperature is preferably within the temperature range at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a film surface such as a coating film, it is expected that the liquid crystal expression temperature on the coating film surface is lower than the liquid crystal expression temperature when a photosensitive side chain type polymer that exhibits liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation of polarized ultraviolet rays is preferably a temperature lower by 10° C. than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer used, and 10° C. lower than the upper limit of the liquid crystal temperature range. The temperature in °C is the temperature in the range of the upper limit. When the heating temperature is lower than the above temperature range, there is a tendency that the anisotropic amplification effect by heat in the coating film is insufficient. In addition, when the heating temperature is too high compared with the above temperature range, the state of the coating film may be close to anisotropy. It tends to be in an isotropic liquid state (isotropic phase). In this case, it may be difficult to reorient in one direction due to self-assembly.

It should be noted that the liquid crystal display temperature refers to: the glass transition temperature (Tg) at which the surface of the side chain type polymer or coating film undergoes phase transition from the solid phase to the liquid crystal phase (Tg), and from the liquid crystal phase to the homogeneous phase (isotropic phase) ) The temperature below the homogeneous phase transition temperature (Tiso) at which phase transition occurs.

From the same reason as described in the step [I], the thickness of the coating film formed after heating may be preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm.

<Process [IV]>

In step [IV], the coating film heated in step [III] is cooled to a temperature lower than the glass transition temperature of the surface of the coating film, and then heated to a temperature higher than the glass transition temperature.

That is, the coating film obtained by heating in the step [III] is once cooled to a temperature lower than the glass transition temperature of the coating film surface. In other words, by cooling the coating film obtained by heating in step [III] to a temperature lower than the lower limit of the liquid crystal expression temperature on the surface of the coating film, the liquid crystal state of the coating film surface is phase-transformed (glass transition) to a solid state . Here, since the liquid crystal expression temperature on the surface of the coating film tends to be lower than the liquid crystal expression temperature when the side chain type polymer is observed as a whole, the cooling temperature of the coating film is preferably lower than that of the glass of the side chain type polymer as the component (A). The temperature at which the transition point temperature (Tg) is lower than 10°C. A preferable example of the cooling temperature is room temperature (for example, 25° C.).

The coating film obtained by heating in step [III] may be actively cooled to a target cooling temperature using a cooling chamber, a cooling material, or the like, or may be slowly cooled by taking it out from the heating means and leaving it to stand.

Furthermore, in process [IV], the cooled coating film is reheated to the temperature more than the glass transition temperature of the coating film surface. Specifically, the cooled coating film is reheated to the liquid crystal expression temperature of the coating film surface. As mentioned above, the liquid crystal expression temperature of the coating film surface means the temperature more than the glass transition temperature of the coating film surface and less than the homogeneous phase transition temperature of the coating film surface. The heating temperature of the coating film after irradiating polarized ultraviolet rays (the heating temperature of step [III]) and the heating temperature at the time of reheating after cooling may be different or the same. The temperature below the heating temperature.

By having the above steps, in the production method of the present invention, efficient introduction of anisotropy to the coating film can be realized. Moreover, the board|substrate with a liquid crystal aligning film can be manufactured efficiently.

<Process [V]>

The [V] step is to place the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a transverse electric field obtained in [IV] in the same manner as above-mentioned [I'] to [III'] or [I'] The substrate with a liquid crystal aligning film (second substrate) obtained in [IV'] without a conductive film is arranged facing each other so that the liquid crystal aligning films of the two face each other through the liquid crystal, and a liquid crystal cell is produced by a known method, This is the process of making a transverse electric field driven liquid crystal display element. It should be noted that, in steps [I'] to [III']] or steps [I'] to [IV'], except that in step [I], a substrate that does not have a conductive film for driving a transverse electric field is used instead of having Except for the substrate of the conductive film for driving a transverse electric field, it can be performed in the same manner as steps [I] to [III] or steps [I'] to [IV']. The difference between steps [I]-[IV] and steps [I']-[IV'] lies in the presence or absence of the above-mentioned conductive film, so the description of steps [I']-[IV'] is omitted.

If a production example of a liquid crystal unit or a liquid crystal display element is cited, the following method can be illustrated: prepare the above-mentioned first substrate and the second substrate, spread spacers on the liquid crystal alignment film of one substrate, and use the liquid crystal alignment film surface as The inner side is pasted to another substrate, and the liquid crystal is injected under reduced pressure and sealed; or the liquid crystal is dropped on the surface of the liquid crystal alignment film where the spacers are scattered, and the substrate is pasted and sealed. In this case, it is preferable to use a substrate having an electrode having a comb-tooth structure for driving a transverse electric field as one of the substrates. The spacer diameter at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, a polymer composition is apply|coated on a board|substrate to form a coating film, and polarized ultraviolet-ray is irradiated. Next, by heating, efficient introduction of anisotropy into the side chain type polymer film is realized, and the board|substrate with a liquid crystal aligning film equipped with the liquid crystal orientation control capability is manufactured.

In the coating film used in the present invention, efficient introduction of anisotropy into the coating film is achieved by utilizing the principle of molecular reorientation induced by photoreaction of side chains and self-assembly based on liquid crystallinity. In the production method of the present invention, when the side-chain type polymer has a structure having a photocrosslinkable group as a photoreactive group, after forming a coating film on the substrate using the side-chain type polymer, irradiate polarized ultraviolet rays, and then heat After that, a liquid crystal display element is produced.

Hereinafter, an embodiment using a side-chain type polymer having a photocrosslinkable group as a photoreactive group is referred to as a first embodiment, and the use of a polymer having a photo-Fries rearrangement group or a different An embodiment of a side chain type polymer having a structured group as a photoreactive group will be described as a second embodiment.

Fig. 1 schematically illustrates a method for producing a liquid crystal aligning film in which a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is used in the first embodiment of the present invention. A diagram of an example of anisotropy introduction processing. Fig. 1 (a) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and Fig. 1 (b) is a diagram schematically illustrating the state of the side chain type polymer film after polarized light irradiation The state diagram, Fig. 1 (c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is small, that is, in the first aspect of the present invention, [ II] A schematic diagram of the case where the ultraviolet irradiation dose in the process is within the range of 1% to 15% of the maximum ultraviolet irradiation dose for ΔA.

Fig. 2 schematically illustrates a method for producing a liquid crystal aligning film in which a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is used in the first embodiment of the present invention. A diagram of an example of anisotropy introduction processing. Fig. 2 (a) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and Fig. 2 (b) is a diagram schematically illustrating the state of the side chain type polymer film after polarized light irradiation The state diagram, Fig. 2 (c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is large, that is, in the first embodiment of the present invention, [II] Schematic diagram of the case where the ultraviolet irradiation dose in the step is within the range of 15% to 70% of the ultraviolet irradiation dose for maximizing ΔA.

Fig. 3 schematically illustrates the structure in which a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is used as a photoreactive group in the second embodiment of the present invention The figure of an example of the anisotropy introduction process in the manufacturing method of the liquid crystal aligning film made of the side chain type polymer of . Fig. 3 (a) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and Fig. 3 (b) is a diagram schematically illustrating the state of the side chain type polymer film after polarized light irradiation State diagram, Figure 3 (c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially the introduced anisotropy is small, that is, in the second mode of the present invention, [ II] A schematic diagram of the case where the ultraviolet irradiation dose in the step is within the range of 1% to 70% of the ultraviolet irradiation dose for maximizing ΔA.

Fig. 4 schematically illustrates the use of a side chain type polymer having a photo-Fries rearrangement group represented by the above formula (19) as a photoreactive group in a second embodiment of the present invention. The figure of an example of the anisotropy introduction process in the manufacturing method of the liquid crystal aligning film. Fig. 4 (a) is a diagram schematically illustrating the state of the side chain type polymer film before polarized light irradiation, and Fig. 4 (b) is a diagram schematically illustrating the state of the side chain type polymer film after polarized light irradiation The state diagram, Fig. 4 (c) is a diagram schematically illustrating the state of the side chain type polymer film after heating, especially when the introduced anisotropy is large, that is, in the second embodiment of the present invention, [II] Schematic diagram when the ultraviolet irradiation dose in the step is within the range of 1% to 70% of the ultraviolet irradiation dose for maximizing ΔA.

In the first aspect of the present invention, by introducing anisotropy to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, first, in The coating film 1 is formed on the substrate. As shown in FIG. 1( a ), the coating film 1 formed on the substrate has a structure in which side chains 2 are randomly arranged. Due to the random arrangement of the side chains 2 of the coating film 1, the mesogen components and photosensitive groups of the side chains 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first aspect of the present invention, by introducing anisotropy to the coating film, when the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, in The coating film 3 is formed on the substrate. As shown in FIG. 2( a ), the coating film 3 formed on the substrate has a structure in which side chains 4 are randomly arranged. Due to the random arrangement of the side chains 4 of the coating film 3, the mesogen components and photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second aspect of the present invention, by introducing anisotropy to the coating film, a structure using a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied. In the case of a liquid crystal aligning film of a side chain type polymer, when the ultraviolet irradiation dose in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation dose that maximizes ΔA, first, the coating film 5 is formed on the substrate. As shown in FIG. 3( a ), the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. Due to the random arrangement of the side chains 6 of the coating film 5, the mesogen components and photosensitive groups of the side chains 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, liquid crystal alignment using a side chain polymer having a structure of the photo-Friesian rearrangement group represented by the above formula (19) is applied by introducing anisotropy to the coating film. In the case of a film, when the ultraviolet irradiation dose in the [II] step is within the range of 1% to 70% of the maximum ultraviolet irradiation dose for ΔA, first, the coating film 7 is formed on the substrate. As shown in FIG. 4( a ), the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. Due to the random arrangement of the side chains 8 of the coating film 7, the mesogen components and photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first form of this embodiment, when the ultraviolet irradiation amount in the [II] step is within the range of 1% to 15% of the ultraviolet irradiation amount that makes ΔA the maximum, the isotropic coating film 1 is irradiated with polarized ultraviolet rays. Thereby, as shown in FIG. 1(b), among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group is preferentially generated. Photoreactions such as dimerization. As a result, the density of the photoreacted side chains 2a becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 1 .

In the first form of the present embodiment, the isotropic coating film 3 is irradiated with polarized ultraviolet rays when the ultraviolet irradiation amount in the [II] step is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA. Thus, as shown in (b) of FIG. 2 , among the side chains 4 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 4 a having a photosensitive group is preferentially generated. Photoreactions such as dimerization. As a result, the density of the photoreacted side chains 4 a increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 3 .

In the second form of this embodiment, a liquid crystal aligning film using a side chain type polymer having a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied, When the ultraviolet irradiation dose in the [II] step is within the range of 1% to 70% of the maximum ultraviolet irradiation dose for ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Thereby, as shown in FIG. 3 (b), among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6a having a photosensitive group is preferentially generated. Photoreactions such as Photofries rearrangement. As a result, the density of the photoreacted side chains 6a becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5 .

In the second mode of this embodiment, the coating film using the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (19) is applied, and the ultraviolet irradiation amount in the step [II] is When ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Thereby, as shown in FIG. 4 (b), among the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 8a having a photosensitive group is preferentially generated. Photoreactions such as Photofries rearrangement. As a result, the density of the photoreacted side chains 8 a increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 7 .

Next, in the first form of this embodiment, when the ultraviolet irradiation amount in the [II] step is within the range of 1% to 15% of the ultraviolet irradiation amount that makes ΔA the maximum, the coating film 1 after irradiating polarized light is heated to produce into a liquid crystal state. Thereby, as shown in FIG. 1(c), in the coating film 1, the amount of crosslinking reaction that occurs is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays. . At this time, the amount of crosslinking reaction occurring in a direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, so the crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is higher than that in the direction parallel to the polarization direction of the irradiated ultraviolet rays, self-assembly occurs in the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains containing the mesogen components 2 for reorientation. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and larger anisotropy is imparted to the coating film 1 .

Similarly, in the first form of this embodiment, when the ultraviolet irradiation amount in the [II] step is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 3 after polarized light irradiation is heated to Made into a liquid crystal state. Thus, as shown in (c) of FIG. 2 , in the side chain type polymer film 3 , crosslinking occurs between a direction parallel to the polarization direction of the irradiated ultraviolet rays and a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The amount of response varies. Therefore, self-assembly occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chains 4 including the mesogen component are re-aligned. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3 .

Similarly, in the second mode of the present embodiment, a coating film using a side chain type polymer having a photoisomerizable group or a photofries rearrangement group represented by the above formula (18) is applied. When the ultraviolet irradiation dose in the [II] step is within the range of 1% to 70% of the maximum ultraviolet irradiation dose for ΔA, the coating film 5 irradiated with polarized light is heated to be in a liquid crystal state. Thereby, as shown in FIG. 3(c), in the coating film 5, between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays, the light Friese rearrangement occurs. The amount of response varies. At this time, the liquid crystal alignment force of the photo-Fries rearrangement body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than that of the side chain before the reaction, so self-assembly occurs in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays , the side chains 6 including the mesogen component undergo reorientation. As a result, the very small anisotropy of the coating film 5 induced by the photo-Fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5 .

Similarly, in the second mode of the present embodiment, the coating film using the side chain type polymer having the structure of the photofries rearrangement group represented by the above formula (19) is applied, and the ultraviolet irradiation in the step [II] When the amount is within the range of 1% to 70% of the ultraviolet irradiation amount that makes ΔA the maximum, the coating film 7 after polarized light irradiation is heated to be in a liquid crystal state. Thus, as shown in (c) of FIG. 4 , in the side chain type polymer film 7, the light generated between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular to the polarization direction of the irradiated ultraviolet rays The amount of the Lys rearrangement varies. The photo-Fries rearrangement body 8 (a) has stronger anchoring force than the side chain 8 before rearrangement, so when a certain amount or more of the photo-Fries rearrangement body is produced, the self-rearrangement occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays. Assembled, the side chains 8 including the mesogen component are re-aligned. As a result, the small anisotropy of the coating film 7 induced by the photo-Fries rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7 .

Therefore, anisotropy can be efficiently introduced into the coating film used by the method of this invention by sequentially irradiating a coating film with polarized ultraviolet rays and heat-processing, and can be made into the liquid crystal aligning film excellent in orientation control ability.

In addition, for the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays irradiated to the coating film and the heating temperature of the heat treatment are optimized. This enables efficient introduction of anisotropy into the coating film.

For efficiently introducing anisotropy into the coating film used in the present invention, the optimal amount of irradiation of polarized ultraviolet light corresponds to causing photocrosslinking reaction, photoisomerization reaction or photosensitive group in the coating film. The amount of Fries rearrangement reaction achieves the optimal amount of polarized UV exposure. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, if there are few photosensitive groups in the side chains that undergo photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction, sufficient photoreaction amount cannot be achieved . In this case, even if heating is performed thereafter, sufficient self-assembly will not proceed. On the other hand, for the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to a structure having a photocrosslinkable group, when the photosensitive group of the side chain undergoing a crosslinking reaction is excessive, the distance between the side chains The cross-linking reaction will be over-propelled. At this time, the resulting film becomes rigid, which may hinder subsequent progress of self-assembly by heating. In addition, for the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to the structure having the photo-Fries rearrangement group, the photosensitive group of the side chain that undergoes the photo-Fries rearrangement reaction becomes excessive. When , the liquid crystallinity of the coating film will decrease excessively. In this case, the liquid crystallinity of the obtained film is also lowered, and the subsequent progress of self-assembly by heating may be hindered. Furthermore, when polarized ultraviolet rays are irradiated to a structure having a photo-Fries rearrangement group, if the irradiation amount of ultraviolet rays is too high, the side chain type polymer may be photodecomposed, which may hinder the subsequent progress of self-assembly by heating. .

Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group of the side chain to undergo photocrosslinking reaction, photoisomerization reaction or photofries rearrangement reaction due to the irradiation of polarized ultraviolet rays is preferably set to It is 0.1 mol% - 40 mol% of the photosensitive group which this side chain type polymer film has, More preferably, it is 0.1 mol% - 20 mol%. By setting the amount of the photosensitive group of the side chain that undergoes photoreaction within such a range, self-assembly in the subsequent heat treatment can be efficiently advanced, and efficient anisotropy in the film can be formed.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the photocrosslinking reaction, photoisomerization reaction or photosensitive group in the side chain of the side chain type polymer film are optimized. The amount of the Fries rearrangement reaction. In addition, efficient introduction of anisotropy into the coating film used in the present invention is realized together with subsequent heat treatment. In this case, the appropriate amount of polarized ultraviolet rays can be performed based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet rays after irradiation with polarized ultraviolet rays were measured. ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays in the coating film, was evaluated from the measurement results of ultraviolet absorption. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays to realize it were obtained. In the manufacturing method of this invention, the amount of polarized ultraviolet rays which realize|achieves this ΔAmax as a reference can determine the preferable amount of polarized ultraviolet rays irradiated in manufacture of a liquid crystal aligning film.

In the production method of the present invention, it is preferable to set the irradiation amount of polarized ultraviolet rays irradiated to the coating film used in the present invention within a range of 1% to 70%, more preferably 1% to 70% of the amount of polarized ultraviolet rays that will realize ΔAmax. 50% range. In the coating film used in the present invention, the amount of irradiation of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays that will realize ΔAmax corresponds to the photosensitive group that the side chain type polymer film has. The amount of polarized ultraviolet rays in which the photocrosslinking reaction occurs is 0.1 mol % to 20 mol % of the whole.

As described above, in the production method of the present invention, in order to efficiently introduce anisotropy into the coating film, an appropriate heating temperature as described above may be determined based on the liquid crystal temperature range of the side chain type polymer. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100°C to 200°C, it is desirable to set the heating temperature after irradiation with polarized ultraviolet rays to 90°C to 190°C. By setting in this way, larger anisotropy is imparted to the coating film used for this invention.

By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.

As above, the substrate for a lateral electric field driven liquid crystal display element manufactured by the method of the present invention or the lateral electric field driven liquid crystal display element having the substrate has excellent reliability and can be suitably used in a large-screen and high-definition liquid crystal television. Wait.

Example

Abbreviations used in Examples are shown below.

(methacrylic monomer)

MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546).

MA2 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).

(Organic solvents)

THF: Tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: Butyl cellosolve

(polymerization initiator)

AIBN: 2,2'-Azobisisobutyronitrile

[Measurement of Phase Transition Temperature]

The liquid crystal phase transition temperature of the polymer obtained in the examples was measured using differential scanning calorimetry (DSC) DSC3100SR (manufactured by Mac Systems).

<Synthesis Example 1>

MA1 (15.29 g, 46 mmol) and MA2 (56.37 g, 184 mmol) were dissolved in THF (655.1 g), and after degassing with a diaphragm pump, AIBN (1.13 g, 6.9 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 20 hours, and the polymer solution of the methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (7000 ml), and the resulting precipitate was filtered. This deposit was wash|cleaned with diethyl ether, and it dried under reduced pressure in 40 degreeC oven, and obtained the methacrylate polymer powder. The polymer had a number average molecular weight of 15,000 and a weight average molecular weight of 40,500.

The liquid crystal phase transition temperature of the obtained methacrylate polymer was 120°C to 185°C.

NMP (54.0g) was added to the obtained methacrylate polymer powder (6.0g), and it stirred and melt|dissolved at room temperature for 5 hours. BC (40.0g) was added and stirred to this solution, and the liquid crystal aligning agent (A) was obtained.

<Example 1>

(Production of liquid crystal unit)

Using the liquid crystal aligning agent (A) obtained in the synthesis example 1, preparation of the liquid crystal cell was performed by the procedure shown below.

The substrate was a glass substrate with a size of 30 mm×40 mm and a thickness of 0.7 mm, and a substrate on which comb-shaped pixel electrodes formed by patterning an ITO film were arranged was used. The pixel electrode has a comb-tooth shape formed by arranging a plurality of "<"-shaped electrode elements bent at the center. The width in the width direction of each electrode element was 10 μm, and the interval between electrode elements was 20 μm. The pixel electrode forming each pixel is formed by arranging a plurality of "<"-shaped electrode elements bent at the center. Therefore, the shape of each pixel is not a rectangular shape, but has an electrode element bent at the center, Similar to the bold "<" shape. Each pixel is divided up and down with the central curved portion as a boundary, and has a first region above the curved portion and a second region below the curved portion. When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is taken as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle (clockwise) of +15°, and in the second region of the pixel In , the electrode elements of the pixel electrode are formed to form an angle of -15° (clockwise). That is, the first region and the second region of each pixel are configured such that directions of in-plane rotation (plane switching) of the liquid crystal induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.

The liquid crystal aligning agent (A) obtained in the synthesis example 1 was spin-coated on the prepared said board|substrate with an electrode. Next, it dried for 90 second with the hot plate of 70 degreeC, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, after irradiating the coating film surface with 313nm ultraviolet rays at 10mJ/ ^cm2 through the polarizing plate, it was heated on a hot plate at 150°C for 10 minutes (first firing), and the substrate that was slowly cooled (cooled) to room temperature was heated again at 150°C. The substrate with a liquid crystal aligning film was obtained by heating on a hot plate at a temperature of 10° C. for 10 minutes (baking twice). In the same manner, different substrates were produced at intervals of 10 mJ/cm ² between 10 mJ/cm ² and 100 mJ/cm ² , and at intervals of 50 mJ/cm ² above 100 mJ/cm ² .

In addition, as a counter substrate, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm without forming an electrode, and an orientation treatment was performed. A sealing agent (manufactured by Kyoritsu Chemical Co., Ltd., XN-1500T) was printed on the liquid crystal aligning film of one board|substrate. Next, after affixing the other board|substrate so that the liquid crystal aligning film surface faced and the orientation direction became 0 degree|times, the sealant was heat-hardened, and the empty cell was produced. Liquid crystal MLC-2041 (manufactured by MERCK CORPORATION) was injected into the empty cell by a depressurized injection method, and the injection port was sealed to obtain a liquid crystal cell having a liquid crystal display element in an IPS (In-Planes Switching) mode.

(orientation observation)

A liquid crystal cell was produced by the method described above. Thereafter, a reorientation treatment was performed in an oven at 120° C. for 60 minutes. Thereafter, observation was performed with a polarizing microscope in which a polarizing plate was in a crossed prism state. When the liquid crystal cell was rotated to show black, the state in which there were no bright spots and poor orientation was regarded as good. Regarding the irradiation amount of ultraviolet rays, as mentioned above, the results of observing the orientation of each different substrate, the irradiation amount boundaries with good orientation are as shown in Table 1.

<Example 2>

A liquid crystal cell was produced by the method similar to Example 1 except having set the temperature of the secondary baking process to 130 degreeC. Orientation was evaluated by the method similar to Example 1 using the obtained liquid crystal cell.

The results are shown in Table 1.

<Comparative examples 1 to 2>

A liquid crystal cell was produced by the same method as in Example 1 except that there was no slow cooling step and no secondary firing treatment. Orientation was evaluated by the method similar to Example 1 using the obtained liquid crystal cell.

The evaluation results are summarized in Table 1.

The results are shown in Table 1.

[Table 1]

According to the result, the boundary of the UV irradiation amount which showed favorable liquid-crystal orientation expanded on the conditions of performing 2nd baking through a slow cooling process.

This is presumed to be because the orientation of the main polymer skeleton is determined by the first firing, but after cooling to a temperature lower than the glass transition temperature, the temperature of the first firing is higher than the clearing point or near the clearing point. The oligomer component and the low molecular weight component exhibited a glass state while maintaining a disordered orientation state (Comparative Examples 1 and 2). Here, it is thought that when heating again at a temperature above the glass transition temperature and below the liquid crystal clearing point, only oligomer components and low molecular weight components follow the orientation orientation of the main polymer skeleton determined by one firing rearrangement in the form of the alignment film, thereby improving the orientation of the entire alignment film. (It should be noted that these are theoretical speculations and do not limit the present invention).

Explanation of reference signs

figure 1

1 side chain type polymer membrane

2. 2a side chain

figure 2

3 side chain type polymer membrane

4. 4a side chain

image 3

5 side chain type polymer membrane

6. 6a side chain

Figure 4

7 side chain type polymer membrane

8. 8a side chain

Claims (17)

1. have the manufacture method that the driving liquid crystal of transverse electric field represents the substrate of element liquid crystal orientation film, it obtains being endowed the described liquid crystal orientation film of tropism control ability by possessing following operation:

[I] polymer composition is coated on there is transverse electric field driving conducting film substrate on and form the operation of film, described polymer composition contains: (A) shows photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property in specific temperature range;

[II] irradiates the operation of polarized UV rays to the film obtained in [I];

The film obtained in [II] is carried out the operation heated by [III]; And

After the film of heating in [III] is cooled to the temperature of the glass transition temperature of this film coated surface not enough by [IV], then be heated to the operation of temperature of more than this glass transition temperature.

2. method according to claim 1, wherein, the chilling temperature of the film in [IV] operation is the temperature than low more than 10 DEG C of side chain type high molecular glass transition point temperature (Tg) as (A) composition.

3. method according to claim 1 and 2, wherein, the heating-up temperature of the film after Ultraviolet radiation and cooled heating-up temperature are again more than the glass transition temperature of film coated surface and the temperature of the homogeneous phase transition temperature of not enough film coated surface.

4. the method according to any one of claims 1 to 3, wherein, (A) composition has the photonasty side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.

5. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (1) ~ (6),

In formula, A, B, D represent singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

S is the alkylidene of carbon number 1 ~ 12, and the hydrogen atom being bonded to them is optionally replaced by halogen group;

T is the alkylidene of singly-bound or carbon number 1 ~ 12, and the hydrogen atom being bonded to them is optionally replaced by halogen group;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

Y ₂for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination, be bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

R represents the alkoxy of hydroxyl, carbon number 1 ~ 6, or represents and Y ₁identical definition;

When X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, the quantity of-CH=CH-CO-O-or-O-CO-CH=CH-, X reaches 2, X is optionally same to each other or different to each other;

Cou represents Coumarin-6-Ji or coumarin-7-Ji, is bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

One in q1 and q2 is 1, and another one is 0;

Q3 is 0 or 1;

P and Q is independently of one another for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination; Wherein, when X is-CH=CH-CO-O-,-O-CO-CH=CH-, P or Q of the side of-CH=CH-institute bonding is aromatic rings, and when the quantity of P reaches more than 2, P is optionally same to each other or different to each other, and when the quantity of Q reaches more than 2, Q is optionally same to each other or different to each other;

L1 is 0 or 1;

L2 is the integer of 0 ~ 2;

When l1 and l2 is 0, when T is singly-bound, A also represents singly-bound;

When l1 is 1, when T is singly-bound, B also represents singly-bound;

H and I is independently of one another for being selected from the group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination.

6. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (7) ~ (10),

In formula, A, B, D represent singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

When X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, the quantity of-CH=CH-CO-O-or-O-CO-CH=CH-, X reaches 2, X is optionally same to each other or different to each other;

L represents the integer of 1 ~ 12;

M represents the integer of 0 ~ 2, and m1, m2 represent the integer of 1 ~ 3;

N represents the integer of 0 ~ 12, and wherein, during n=0, B is singly-bound;

Y ₂for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 ~ 8 and their combination, be bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

R represents the alkoxy of hydroxyl, carbon number 1 ~ 6, or represents and Y ₁identical definition.

7. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (11) ~ (13),

In formula, A represents singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

When X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, the quantity of-CH=CH-CO-O-or-O-CO-CH=CH-, X reaches 2, X is optionally same to each other or different to each other;

L represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2, and m1 represents the integer of 1 ~ 3;

R represents the ring in the ester ring type hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and the carbon number 5 ~ 8 being selected from 1 valency, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5, or R represents the alkoxy of hydroxyl or carbon number 1 ~ 6.

8. the method according to any one of Claims 1 to 4, wherein, (A) composition has following formula (14) or the photonasty side chain shown in (15),

In formula, A represents singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

L represents the integer of 1 ~ 12, and m1, m2 represent the integer of 1 ~ 3.

9. the method according to any one of Claims 1 to 4, wherein, (A) composition as shown in following formula (16) or (17),

In formula, A represents singly-bound ,-O-,-CH ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

When X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, the quantity of-CH=CH-CO-O-or-O-CO-CH=CH-, X reaches 2, X is optionally same to each other or different to each other;

L represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2.

10. the method according to any one of Claims 1 to 4, wherein, (A) composition has any one the photonasty side chain in the group being selected from and being made up of following formula (18) or (19),

In formula, A, B represent singly-bound ,-O-,-CH independently of one another ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

One in q1 and q2 is 1, and another one is 0;

L represents the integer of 1 ~ 12, and m1, m2 represent the integer of 1 ~ 3;

R ₁represent hydrogen atom ,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or the alkoxy of carbon number 1 ~ 5.

11. methods according to any one of Claims 1 to 4, wherein, (A) composition has the photonasty side chain shown in following formula (20),

In formula, A represents singly-bound ,-O-,-CH ₂-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-;

Y ₁represent the ring in the ester ring type hydrocarbon of the phenyl ring of 1 valency that is selected from, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5 ~ 8, or be selected from the group of 2 ~ 6 the identical or different rings in these substituting groups by binding groups B bonding, be bonded to their hydrogen atom independently of one another optionally by-COOR ₀,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace, in formula, R ₀represent the alkyl of hydrogen atom or carbon number 1 ~ 5;

When X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, the quantity of-CH=CH-CO-O-or-O-CO-CH=CH-, X reaches 2, X is optionally same to each other or different to each other;

L represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2.

12. methods according to any one of claim 1 ~ 11, wherein, (A) composition has any one the liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (21) ~ (31),

In formula, A and B has definition same as described above;

Y ₃for being selected from the group in the group that is made up of the ester ring type hydrocarbon of the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring and carbon number 5 ~ 8 and their combination, be bonded to their hydrogen atom independently of one another optionally by-NO ₂,-CN, halogen group, the alkyl of carbon number 1 ~ 5 or carbon number 1 ~ 5 alkoxy replace;

R ₃represent hydrogen atom ,-NO ₂,-CN ,-CH=C (CN) ₂,-CH=CH-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen heterocyclic ring, the ester ring type hydrocarbon of carbon number 5 ~ 8, the alkyl of carbon number 1 ~ 12 or carbon number 1 ~ 12 alkoxy;

One in q1 and q2 is 1, and another one is 0;

L represents the integer of 1 ~ 12, m represents the integer of 0 ~ 2, wherein, in formula (23) ~ (24), the summation of all m is more than 2, in formula (25) ~ (26), the summation of all m is the integer that more than 1, m1, m2 and m3 represent 1 ~ 3 independently of one another;

R ₂represent hydrogen atom ,-NO ₂,-CN, halogen group, the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, the ester ring type hydrocarbon of nitrogen heterocyclic ring and carbon number 5 ~ 8 and alkyl or alkoxy;

Z ₁, Z ₂represent singly-bound ,-CO-,-CH ₂o-,-CH=N-,-CF ₂-.

13. 1 kinds of substrates having the driving liquid crystal of transverse electric field and represent element liquid crystal orientation film, it is manufactured by the method according to any one of claim 1 ~ 12.

14. 1 kinds of driving liquid crystal of transverse electric field represent element, and it has substrate according to claim 13.

15. 1 kinds of driving liquid crystal of transverse electric field represent the manufacture method of element, and it obtains this liquid crystal by possessing following operation and represents element:

Prepare the substrate according to claim 13 i.e. operation of the 1st substrate;

Obtain and have the operation of the 2nd substrate of following liquid crystal orientation film, it is by possessing following operation [I '], [II '] and [III '] and obtain being endowed the liquid crystal orientation film of tropism control ability; And

[V] with described 1st liquid crystal orientation film and the 2nd liquid crystal orientation film across the right mode of liquid crystal phase, subtend described 1st substrate of configuration and the 2nd substrate, thus the operation obtaining that liquid crystal represents element,

Described operation [I '], [II '] and [III '] be:

[I '] coated polymeric composition and form the operation of film on the 2nd substrate, described polymer composition contains: (A) shows photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property in specific temperature range;

[II '] irradiates the operation of polarized UV rays to the film obtained in [I ']; And

The film obtained in [II '] is carried out the operation heated by [III '].

16. methods according to claim 15, wherein, the operation obtaining described 2nd substrate also has [IV '] by after in [III '], the film of heating is cooled to the temperature of the glass transition temperature of this film coated surface not enough, then is heated to the operation of temperature of more than this glass transition temperature.

17. 1 kinds of driving liquid crystal of transverse electric field represent element, and it is manufactured by the method described in claim 15 or 16.