CN106232733A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element - Google Patents

Abstract

According to the present invention, there are provided a lateral electric field driven liquid crystal display element which is endowed with high efficiency of orientation control ability and excellent in image sticking characteristics, and a novel composition for producing the liquid crystal display element. The present invention solves the above-mentioned problems by a composition containing: (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range; A compound having at least one nitrogen atom bonded to a hydroxyalkyl group, and (C) an organic solvent.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

technical field

The present invention relates to a liquid crystal aligning agent for producing a transverse electric field drive type liquid crystal display element, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal aligning film. More specifically, it relates to a novel composition for producing a liquid crystal display element excellent in image sticking properties.

Background technique

It is known that liquid crystal display elements are light in weight, thin in cross-section, and low in power consumption, and have achieved remarkable development in recent years, such as being used for large-scale television applications. The liquid crystal display element is constituted by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes, for example. 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 can be utilized 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 anisotropically decomposed 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 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 a side chain-type polymer having azobenzene is used in the side chain, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene moiety in the side chain parallel to the polarized light, The liquid crystal is aligned 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. Shadt 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 as when using the brush rubbing method, a large amount of polarized light irradiation may be required, and 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 or 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 is a concern that poor alignment and image sticking may occur. In particular, in a lateral electric field driven liquid crystal display element, the liquid crystal molecules are switched in-plane, so liquid crystal orientation shift after liquid crystal driving is likely to occur, and display afterimage caused by AC driving becomes a significant problem.

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

The object of this invention is to provide the liquid crystal aligning agent used for manufacture of a liquid crystal display element, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element using this liquid crystal aligning film.

solutions to problems

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

<1> a polymer composition, which contains:

(A) A photosensitive side chain type polymer that exhibits liquid crystallinity in a specific temperature range,

(B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule,

as well as

(C) Organic solvents.

<2> In the above <1>, the component (A) may have a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofries rearrangement.

<3> In the above <1> or <2>, the compound having 2 to 6 nitrogen atoms to which at least one hydroxyalkyl group is bonded in one molecule as the component (B) can be represented by the following formula (b): .

(In the formula, R ¹ is an organic group of n valence,

L ¹ represents a single bond, an alkylene group with 1 to 10 carbons or NX ¹ ; X ¹ represents a hydrogen atom or an alkyl group, in addition, X ¹ optionally forms an alkylene group together with other X ¹ , and X ¹ optionally passes Bonding with R1 to form ^a ring structure;

L ² represents a single bond or an alkylene group with 1 to 10 carbons;

L ³ represents a single bond, NH or N-alkyl;

L ⁴ represents a single bond or an alkylene group with 1 to 10 carbons;

L5 represents a single bond or carbonyl ^; when L3 is NH or N ^- alkyl, ^L4 and ^L5 are different from each other and represent a single bond;

L ⁶ and L ⁷ each independently represent a linear or branched alkylene group with 2 to 20 carbons;

The alkylene groups in L ¹ , L ² , L ⁴ , L ⁶ and L ⁷ are optionally substituted by one or more substituents selected from halogen and hydroxyl;

n is an integer of 2-6. )

<4> In the above <3>, n may be 2 or 3.

<5> In the above <3> or <4>, at least one of L ⁶ and L ⁷ can be represented by the following formula (b1).

In the formula, R ² to R ⁵ each independently represent any of a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group.

<6> In any one of the above-mentioned <3> to <5>, L ⁶ and L ⁷ in the formula (b) may both represent ethylene groups.

<7> In any one of the above-mentioned <3> to <6>, in R ¹ or L ¹ of formula (b), the atom directly bonded to the carbonyl group of formula (b) may be a carbon atom that does not form an aromatic ring .

<8> In any one of the above-mentioned <3> to <7>, R ¹ in the formula (b) can be represented by the following structure.

<9> In any one of said <1>-<8>, (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 alkyl group 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 The alkyloxy 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 is 2, X can be 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 1-5 carbons or alkyloxy group with 1-5 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 ; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 In the case of the above, P may be the same or different from each other, and when the number of Q is 2 or more, the Q may be 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.

<10> In any one of said <1>-<8>, (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).

<11> In any one of said <1>-<8>, (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.

<12> In any one of said <1>-<8>, (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.

<13> In any one of said <1>-<8>, (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.

<14> In any one of said <1>-<8>, (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 alkyl group with 1 to 5 carbons Oxygen.

<15> In any one of said <1>-<8>, (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.

<16> In any one of <1> to <15> 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 and B 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 alkyloxy 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;

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

l represents an integer from 1 to 12; m represents an integer from 0 to 2, wherein, in formulas (23) to (24), the sum of all m is more than 2, and in formulas (25) to (26), the sum of all m 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 carbon atoms, and Alkyl or alkyloxy;

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

<17> a kind of manufacture method that has the substrate of lateral electric field driven type liquid crystal display element liquid crystal aligning film, it obtains the described liquid crystal aligning film that has been endowed with alignment control ability by possessing following procedure:

[1] The process of coating the composition described in any one of the above <1> to <16> on a substrate having a conductive film for driving a transverse electric field to form a coating film;

[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].

<18> The board|substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by the manufacturing method as described in said <17>.

<19> A lateral electric field driven liquid crystal display element comprising the substrate of the above <18>.

<20> A method of 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 <18> above;

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

[IV] 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 that exhibits liquid crystallinity in a specific temperature range; molecule, (B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and (C) 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'].

<21> A lateral electric field-driven liquid crystal display element manufactured by the above-mentioned <20>.

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 present invention can provide a liquid crystal alignment film with little thermal deterioration even under long-term thermal stress and a method for manufacturing a liquid crystal display element that can stably exhibit high display quality in a high-temperature environment, and is especially suitable for a transverse electric field drive type liquid crystal display element .

The transverse electric field driven liquid crystal display element manufactured by the method of the present invention is endowed with orientation control ability with high efficiency, and therefore, its display characteristics will not be damaged even if it is driven continuously for a long time.

In addition, in the present invention, by making the polymer composition contain (B) component, that is, a compound having 2 to 6 nitrogen atoms to which at least one hydroxyalkyl group is bonded in one molecule, it is possible to form a voltage retention function in a high-temperature environment. A liquid crystal alignment film whose rate does not decrease for a long time. And it is possible to form a liquid crystal aligning film with little change in voltage retention due to firing temperature. That is, even if it receives a long-term thermal stress, it can provide the liquid crystal display element which shows little thermal deterioration and a liquid crystal display element which shows high display quality stably even in a high-temperature environment.

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.

Fig. 4 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 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 of the present invention has a photosensitive side chain polymer (hereinafter also referred to simply as a side chain polymer) capable of exhibiting liquid crystallinity. A film of a photosensitive side chain type polymer. This coating film was not subjected to brushing treatment, but was subjected to orientation treatment by irradiation with polarized light. And after irradiating polarized light, the coating film (henceforth also referred to as a liquid crystal aligning film) provided with orientation control ability is formed through the process of heating this side chain type polymer film. At this time, the slight anisotropy exhibited by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-assembly. As a result, efficient orientation processing is realizable as a liquid crystal aligning film, and the liquid crystal aligning film provided with high orientation control ability can be obtained.

In addition, in the polymer composition of the present invention, in addition to the side chain type polymer as the (A) component and the organic solvent as the (C) component, one molecule of the (B) component has 2 to A compound having 6 nitrogen atoms bonded to at least one hydroxyalkyl group. Accordingly, even in a high-temperature environment for a long period of time, there is little thermal deterioration and a high voltage retention rate is exhibited. And it is possible to form a liquid crystal aligning film with little change in voltage retention due to firing temperature. In particular, the effect is increased by using a specific substance as a compound having 2 to 6 nitrogen atoms bonded with at least one hydroxyalkyl group in one molecule. The inventors of the present invention think that these phenomena are brought by adding (B) component, and (A) component and (B) component exert interaction, thereby dramatically improving the desired effect (it should be noted that These include the inventor's insight into the mechanism of the invention, but do not limit the invention).

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 A photosensitive side chain polymer, (B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and (C) 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].

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.

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

For the second substrate, 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, by using the above steps [I] to [III] (due to using no transverse electric field driving For the sake of convenience, the second substrate having a liquid crystal aligning film endowed with an orientation control ability can be obtained.

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

[IV] 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 [III] and [IV] 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 A chain-type polymer, a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and an organic solvent.

<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, However, It is not limited to these.

Moreover, in the case of a reflective liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, 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; (B) a molecule having 2 to 6 bonds; A compound having at least one hydroxyalkyl nitrogen atom; and (C) 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) It is sufficient that the side chain type polymer reacts with light in the wavelength range of 250 nm to 400 nm and exhibits 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 the wavelength range of 250 nm to 400 nm.

(A) The side chain type polymer preferably has a mesogen group in order to exhibit liquid crystallinity in the temperature range of 100°C to 300°C.

(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 in which a crosslinking reaction or photofries rearrangement occurs in response to light, and is more preferably a structure in which a crosslinking reaction occurs. 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 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 the side chain type polymer is used as a liquid crystal aligning film, stable liquid crystal orientation can be obtained.

The structure of the polymer can be, for example, a structure having 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 azophenyl group, etc. Mesogen components such as mesogens and photosensitive groups that are bonded to the front end and undergo crosslinking reactions and isomerization reactions in response to light; have a main chain and side chains bonded to it, and the side chains have both mesogens 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 capable of expressing 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 alkyl group 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 The alkyloxy 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 is 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 1-5 carbons or alkyloxy group with 1-5 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; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and the number of P is 2 or more , P is optionally the same or different from each other, and when the number of Q is 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, Y1, 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 alkyl group 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 alkyloxy group with 1 to 5 carbons;

R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH═C(CN) ₂ , -CH═CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing 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 from 1 to 12; m represents an integer from 0 to 2, wherein, in formulas (23) to (24), the sum of all m is 2 or more; 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, -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 alkyloxy;

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 refers to 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: the polymerizable group is selected from hydrocarbons, (meth)acrylates, itacron Radical polymerizable groups such as ester, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane at least one of the group consisting of alkanes; and, the photosensitive side chain includes at least one of the above-mentioned formulas (1) to (6), preferably, for example, includes the above-mentioned formulas (7) to (10) At least one photosensitive side chain, a photosensitive side chain comprising at least one of the above formulas (11) to (13), a photosensitive side chain represented by the above formula (14) or (15), the above formula ( 16) or the photosensitive side chain represented by (17), the photosensitive side chain represented by said formula (18) or (19), the photosensitive side chain represented by said formula (20).

[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 structures.

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, acrylate-2,2, 2-Trifluoroethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate ester, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8- Methyl-8-tricyclodecanyl ester, acrylate-8-ethyl-8-tricyclodecanyl ester, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl Anthracenylmethyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl 2-methoxyethyl acrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxymethacrylate Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecane methacrylate Esters, and 8-ethyl-8-tricyclodecanyl methacrylate, 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 butyl)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 Oxidation-2-ethyl cyclohexane 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-dodecane ylcarbazole, 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 ylcarbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxy ylcarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxy carbonyl)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, but when the concentration is too low, it is difficult to obtain a high molecular weight polymer, and when the concentration is too high, the viscosity of the reaction solution becomes too high and it is difficult to stir uniformly, so the monomer concentration is preferably 1% by mass. ~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 is preferably 0.1 mol% to 10 mol% with respect to the polymerizable monomer. 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 exhibiting 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, GPC (Gel Permeation Chromatography, Gel Permeation Chromatography, ) method, the 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, but they may also be mixed and removed 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, which are not photosensitive side chain polymers capable of expressing liquid crystallinity.

<<(B)Ingredient>>

<Compounds having 2 to 6 nitrogen atoms to which at least one hydroxyalkyl group is bonded in one molecule>

The polymer composition used in the present invention contains a compound having 2 to 6 nitrogen atoms bonded with at least one hydroxyalkyl group in one molecule.

This compound will not be specifically limited if any one, or both, or all effects of the following effects i)-iii) are exhibited when the polymer composition used for this invention forms a liquid crystal aligning film. i) Improve the film density of the liquid crystal alignment film, ii) suppress impurities that gradually seep out from the lower part of the liquid crystal alignment film, or iii) achieve improved voltage retention by adsorbing impurities extracted from the liquid crystal with the liquid crystal alignment film .

The aforementioned compound is not particularly limited as long as it has 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule of the compound, and other structures are not particularly limited. From the viewpoint of availability and the like, a preferred example is the following: The compound represented by formula (b).

In formula (b), R ¹ is an organic group with n valence,

L ¹ represents a single bond, an alkylene group with 1 to 10 carbons or NX ¹ ; X ¹ represents a hydrogen atom or an alkyl group; in addition, X ¹ optionally forms an alkylene group together with other X ¹ , and X ¹ optionally passes Bonding with R1 to form ^a ring structure;

L ² represents a single bond or an alkylene group with 1 to 10 carbons;

L ³ represents a single bond, NH or N-alkyl;

L ⁴ represents a single bond or an alkylene group with 1 to 10 carbons;

L ⁵ represents a single bond or carbonyl, and when L ³ is NH or N-alkyl, L ⁴ and L ⁵ are different and represent a single bond;

L ⁶ and L ⁷ each independently represent a linear or branched alkylene group with 2 to 20 carbons, the alkylene group is optionally substituted by one or more substituents selected from halogen and hydroxyl;

n is an integer of 2-6.

The ⁿ -valent organic group of R in the aforementioned formula (b) refers to an n-valent group obtained by removing n hydrogen atoms from an alkyl group having 2 to 10 carbon atoms, or an aromatic ring or alicyclic hydrocarbon, The aromatic ring or alicyclic hydrocarbon has a 5-membered or 6-membered carbocyclic or heterocyclic ring, or a structure in which 2 to 4 of these rings are bonded or condensed directly or via a bonding group. Here, as a bonding group for linking the ring structure, it represents an alkylene group, an alkenylene group, or an alkynylene group having 1 to 6 carbon atoms, =NR _b (herein, R _b represents a hydrogen atom or a carbon number 1 ~4 alkyl), -S-, -C(O)NH- or -C(O)-O-, except for the aromatic ring or alicyclic hydrocarbon of R ¹ bonded to n L1 groups The carbon atom in is optionally substituted by an oxygen atom, nitrogen atom or sulfur atom, and the hydrogen atom on the carbon atom other than the n L1 groups is optionally substituted by an alkyl group having 1 to 4 carbons or a halogen.

In (b) above, when L1 is ^NX1 , the carbon number of the "alkyl group" of X1 is typically ^1-10 , preferably ^1-6 , more preferably 1-4, even more preferably 1-3 .

It is preferable that the carbon number of the alkylene group of said L1 is ^1-6 .

The number of carbon atoms in the alkylene group of L ² is preferably 2-6.

In (b) above, the carbon number of the "alkyl" of the N-alkyl group in L3 is typically ¹ to 10, preferably 1 to 6, more preferably 1 to 4, even more preferably 1 ~3.

The number of carbon atoms in the alkylene group of L ⁴ is preferably 2-6.

The number of carbon atoms in the alkylene group of L ⁶ and L ⁷ is preferably 2-6.

In the aforementioned formula (b), "halogen" means fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine, more preferably fluorine.

Among them, the atom directly bonded to the carbonyl group in R ¹ of the formula (b) is preferably a carbon atom not forming an aromatic ring from the viewpoint of liquid crystal orientation. In addition, R ¹ in the formula (b) is preferably a group derived from an aliphatic hydrocarbon, and more preferably has 1 to 10 carbon atoms, from the viewpoint of liquid crystal orientation and solubility similarly to the above.

In formula (b), n represents an integer of 2-6, and n is preferably 2-4, more preferably 2 or 3, from the viewpoint of solubility.

In formula (b), as L ⁶ and L ⁷ , from the viewpoint of reactivity, a structure represented by the following formula (b1) is preferable, and an ethylene group is more preferable.

In formula (b1), R ² to R ⁵ each independently represent any of a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group. Here, the "hydrocarbon group" typically represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and preferably represents an alkyl group having 1 to 10 carbon atoms.

In the structure represented by the formula (b), the structure of the R ¹ moiety is preferably a structure selected from the following b2-1 to b2-47. More preferably, they are b2-1 to b2-29.

The structure of the portion bonded to R ¹ is preferably a structure selected from b3-1 to b3-8.

The structure bonded to a carbon atom is preferably b3-1 to b3-8, and the structure bonded to a nitrogen atom is preferably b3-1 to b3-4.

In formula, n2 represents the integer of 1-20, Preferably it is 2-10, Especially preferably, it is 2-7. n3 represents the integer of 1-10, Preferably it is 2-10, Especially preferably, it is 2-7. n4 represents the integer of 2-20, Preferably it is 2-10, Especially preferably, it is 2.

As a specific example of preferable (B) component, the compound of following T1-T9, Primid XL-552, Primid SF-4510 are mentioned, for example.

As a more preferable example of (B) component, the compound of T1-T7 is mentioned.

<Manufacture of compound of formula (b-1)>

The synthetic method of compound (B) is not particularly limited, for the compound shown in following formula (b-1), can be by making the polycarboxylic acid shown in following formula (X2) and following formula (X1) Glycol amine compounds are reacted to manufacture.

plan 1:

Use a solvent that is inert to the reaction as needed, and react the compound represented by the general formula X2 with the glycol amine compound represented by the formula X1 using a condensing agent in the presence of a base as needed, thereby obtaining the formula b- Compounds shown in 1.

The amount of the reaction substrate can be used in an amount of 0.98 to 1.05 equivalents of the diolamine compound represented by the formula X1 with respect to one carboxyl group of the compound represented by the formula X2.

The condensing agent is not particularly limited as long as it is a condensing agent used in general amide synthesis. For example, 1 to 1.5 equivalents of Xiangshan reagent (2-chloro-N-methyl pyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate), etc.

When a solvent is used, the solvent used is not particularly limited as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; Alicyclic hydrocarbons such as alkanes; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloro Ethane, trichloroethylene, tetrachloroethylene and other aliphatic halogenated hydrocarbons; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane and other ethers; ethyl acetate, propane Esters such as ethyl acetate; Amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone; Triethylamine, tributylamine, N,N - Amines such as dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone, or two or more of them may be used in combination.

It is not necessary to add a base. When using a base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, and potassium carbonate in an amount of 1 to 4 equivalents to one carboxyl group of the compound represented by the formula X2 can be used. Alkali metal carbonates, sodium bicarbonate, potassium bicarbonate and other alkali metal bicarbonates, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole , 1,8-diazabicyclo[5,4,0]-7-undecene and other organic bases.

The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, and can be set arbitrarily usually within the range of 5 minutes to 100 hours.

In general, it is preferable to use, for example, 1 to 20 equivalents of the compound represented by the formula X1 and 1 to 4 equivalents of WSC (1-ethyl-3-( 3-Dimethylaminopropyl)-carbodiimide hydrochloride), CDI (carbonyldiimidazole) and other condensing agents, according to the needs in 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4-(di In the presence of a base such as methylamino)pyridine, without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, and carrying out 10 within the range of 0°C to the reflux temperature of these solvents Minutes to 24 hours of response.

In addition, it is also possible to start from the compound represented by the formula X2, through the known methods recorded in the literature, for example, the method of reacting it with chlorinating agents such as thionyl chloride, phosphorus pentachloride or oxalyl chloride; making it react with pivaloyl chloride or Organic acid halides such as isobutyl chloroformate react in the presence of the above-mentioned base if necessary, and then react with compound X1 to synthesize a compound represented by formula b-1.

At this time, the glycol amine compound represented by the formula X1 can be used in an amount of 0.98 to 1.05 equivalents with respect to one carboxyl group of the compound represented by the formula X2, and reacted in the presence of a base if necessary, whereby the formula b- Compounds shown in 1.

When a solvent is used, the solvent used is not particularly limited as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; Alicyclic hydrocarbons such as alkanes; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloro Ethane, trichloroethylene, tetrachloroethylene and other aliphatic halogenated hydrocarbons; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane and other ethers; ethyl acetate, propane Esters such as ethyl acetate; amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N,N-dimethylaniline ; pyridine, picoline and other pyridines; methanol, ethanol, ethylene glycol and other alcohols; acetonitrile, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and water, etc. These solvents may be used alone, or two or more of these may be used in combination.

When a base is used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydroxides such as sodium hydroxide and potassium tert-butoxide in an amount of 1 to 4 equivalents to one ester group of the compound represented by the formula X2 can be used. Alcoholates, lithium diisopropylamide, lithium hexamethyldisilazane, sodium amide and other alkali metal amides, organic metal compounds such as tert-butyllithium, sodium carbonate, potassium carbonate, sodium bicarbonate and other alkali metal carbon salt, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5,4,0]-7 -Organic bases such as undecene, etc.

The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, and can be set arbitrarily usually within the range of 5 minutes to 100 hours.

In general, it is preferable to use 0.98 to 1.05 equivalents of compound X2 with respect to 1 equivalent of amino groups of compound X1 in tetrahydrofuran, 1,4-dioxane, acetonitrile, N,N-dimethylformamide, etc. In the polar solvent, if necessary, 1 to 3 equivalents of sodium hydride, potassium tert-butoxide, potassium hydroxide, potassium carbonate, triethylamine, pyridine, etc. are used as bases with respect to 1 equivalent of amino groups of compound X2. The reaction was carried out in the temperature range of ~90°C for 10 minutes to 24 hours.

<Production of compound of formula (b-2)>

The compound represented by the following formula b-2 can be produced by reacting a polyisocyanate compound represented by the following formula X3 with the above-mentioned compound X1.

Scenario 2:

In the reaction of the isocyanate X3 and the diol amine X1, the amount of the diol amine X1 used may be 0.98 to 1.2 equivalent times relative to one isocyanate group contained in the isocyanate X3. More preferably, it is 1.0 to 1.02 equivalent times.

The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; halogenated solvents such as carbon tetrachloride, chloroform, and 1,2-dichloroethane; Hydrocarbons; diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones; acetonitrile, propionitrile and other nitriles; ethyl acetate, Ethyl propionate and other carboxylic acid esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazole Nitrogen-containing aprotic polar solvents such as ketones; sulfur-containing aprotic polar solvents such as dimethyl sulfoxide and sulfolane; pyridines such as pyridine and picoline, etc. These solvents may be used alone, or two or more of them may be used in combination. Toluene, acetonitrile, and ethyl acetate are preferable, and toluene and ethyl acetate are more preferable.

The usage-amount (reaction concentration) of a solvent is not specifically limited, The reaction can also be performed without using a solvent, and when using a solvent, it can use 0.1-100 mass times of a solvent with respect to an isocyanate compound (C). Preferably it is 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.

The reaction temperature is not particularly limited, and is, for example, -90 to 150°C, preferably -30 to 100°C, more preferably 0 to 80°C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

In order to shorten the reaction time, a catalyst may also be added, and examples thereof include dibutyltin dilaurate, dioctyltin bis(isooctyl mercaptoacetate), dibutyltin bis(isooctyl mercaptoacetate), dibutyltin bis(isooctyl mercaptoacetate), Organotin compounds such as dibutyltin acetate; triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, pyridine, tetramethylbutylenediamine, N -Methylmorpholine, 1,4-diazabicyclo-2.2.2-octane, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3 .0] Nonene-5 and other amines; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid and other organic sulfonic acids; sulfuric acid, phosphoric acid, perchloric acid and other inorganic acids; tetrabutyl titanate, tetraethyl titanate , titanium compounds such as tetraisopropyl titanate; bismuth-based compounds such as bismuth tris(2-ethylhexanoate); quaternary ammonium salts, etc. These catalysts may be used alone or in combination of two or more. In addition, these catalysts are preferably a liquid or a substance soluble in a reaction solvent.

When adding the catalyst, the catalyst can be used in an amount of 0.005 to 100 wt%, preferably 0.05 to 10 wt%, more preferably 0.1 to 5 wt%, based on the total amount (mass) of compounds having isocyanate groups. When an organotin compound, a titanium compound, or a bismuth-based compound is used as a catalyst, it is preferably 0.005 to 0.1 wt%.

The reaction may be carried out under normal pressure or under increased pressure, and may be performed either batchwise or continuously.

<Production of compound of formula (b-3)>

For the compound shown in the following formula b-3, by making the polyamine compound shown in the following formula X4 react with the carboxylic acid shown in the following formula X5, after converting into the polycarboxylic acid shown in the following formula X6, It can be produced by reacting with the diol amine compound represented by the above-mentioned formula X1.

Option 3:

In the reaction of compound X4 and compound X5, the amount of the reaction substrate can be 0.98 to 1.05 equivalents of compound X5 relative to 1 equivalent of amino groups of compound X4.

When a solvent is used, the solvent used is not particularly limited as long as it does not impair the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; Alicyclic hydrocarbons such as alkanes; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloro Ethane, trichloroethylene, tetrachloroethylene and other aliphatic halogenated hydrocarbons; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane and other ethers; ethyl acetate, propane Esters such as ethyl acetate; amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N,N-dimethylaniline ; pyridine, picoline and other pyridines; methanol, ethanol, ethylene glycol and other alcohols; acetonitrile, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and water, etc. These solvents may be used alone, or two or more of them may be used in combination.

When using a base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alcohols such as sodium ethoxide and potassium tert-butoxide in an amount of 1 to 4 equivalents to one amino group of the compound represented by formula X4 can be used. Alkali metal amides such as salts, lithium diisopropylamide, lithium hexamethyldisilazane, sodium amide, organometallic compounds such as tert-butyllithium, alkali metal carbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate salt, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5.4.0]undecene and other organic bases.

The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, and can be set arbitrarily usually within the range of 5 minutes to 100 hours.

In general, it is preferred, for example, to use compound X4 and 0.98 to 1.05 equivalents of compound X5 relative to 1 equivalent of amino groups of compound X4 in tetrahydrofuran, 1,4-dioxane, acetonitrile, N,N-dimethyl In a polar solvent such as methyl formamide, 1 to 3 equivalents of sodium hydride, potassium tert-butoxide, potassium hydroxide, potassium carbonate, triethylamine, pyridine, etc. are used as necessary with respect to 1 equivalent of amino groups of compound X4 as The base is reacted at a temperature range of 0 to 90° C. for 10 minutes to 24 hours.

The conditions for the reaction of Compound X6 and Compound X1, the equivalent weight of the substrate, etc. are based on the above conditions for the reaction of Compound X2 and Compound X1.

<Production of compound of formula (b-4)>

For the compound shown in the following formula b-4, by making the polyamine compound shown in the following formula X4 react with the acid halide shown in the following formula X7, after obtaining the polyamide shown in the following formula X8, make it It can be produced by reacting with the diol amine compound represented by the above-mentioned formula X1.

Option 4:

Compound X7 can be obtained by reacting the above-mentioned compound X5 with a known method, for example, by reacting with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, or reacting with an organic acid such as pivaloyl chloride or isobutyl chloroformate. The halogenated compound is obtained by reacting in the presence of the above-mentioned base as needed. The reaction conditions for the reaction of X7 and X4, the equivalent weight of the substrate, etc. are based on the reaction conditions of the above-mentioned compound X2 and compound X1.

<Production of compound of formula (b-5)>

For the compound represented by the following formula b-5, by making the acrylic acid derivative represented by the following formula X9 react with the above-mentioned compound X1, after converting into the compound represented by the following formula X10, make it react with the compound represented by the above-mentioned formula X4 The polyamine compound reaction, which can be produced.

Option 5:

<Production of compound of formula (b-6)>

For the compound represented by the following formula b-6, by reacting the acrylic acid derivative represented by the above-mentioned formula X9 with the above-mentioned compound X4, after converting it into a compound represented by the following formula X11, reacting it with the above-mentioned compound X1, thereby can be manufactured.

Option 6:

<Manufacture of other compounds of formula (b)>

Then, by applying the above-mentioned reaction conditions, various compounds (B) can be synthesized.

It should be noted that, in the above formulas X1 to X9 and b-1 to b-6, R ¹ , n2, L ⁶ , L ⁷ and n represent the same meanings as above, and J represents a chlorine atom, a bromine atom, an iodine atom, C ₁ -C ₄ alkylcarbonyloxy group (for example, pivaloyloxy group), C ₁ -C ₄ alkylsulfonate group (for example, methanesulfonyloxy group), C ₁ -C ₄ haloalkylsulfonic acid Ester group (for example, trifluoromethanesulfonyloxy), arylsulfonate group (for example, benzenesulfonyloxy, p-toluenesulfonyloxy) or azole group (for example, imidazol-1-yl) and the like Good leaving group, J ² represents Cl, etc., J ³ represents alkoxy groups such as methoxy and ethoxy.

When there are too many compounds having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, it will cause adverse effects from the viewpoint of not showing sufficient liquid crystal orientation control force and solubility, and when it is too small, The effect of the present invention cannot be obtained. Therefore, the addition amount of the compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the polymer of component (A). quality%.

<<(C)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-dimethylimidazolinone, 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 Base-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), (B) and (C) components. As its example, can enumerate the solvent that is used to improve film thickness uniformity, surface smoothness when coating polymer composition, compound, the compound that is used to improve the adhesiveness of liquid crystal aligning film and substrate etc., but not limited to here.

Specific examples of the solvent (poor solvent) for improving 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 Monomethyl 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-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, 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, acetic acid Ethyl ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 1-methoxy-2-propionate Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 - monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, Solvents with low surface tension such as n-propyl lactate, n-butyl lactate, and isoamyl lactate, etc.

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 the compound for improving film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.

More specifically, examples thereof include Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products Corporation), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC CORPORATION), 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 SEIMICHEMICAL 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 for improving 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. Preference is given to colorless sensitizers and triplet sensitizers.

As photosensitizers, there are aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), coumarin ketone, carbonyl bis Coumarins, aromatic-2-hydroxyketones, and aromatic-2-hydroxyketones substituted by amino groups (2-hydroxybenzophenone, mono-p-(dimethylamino)-2-hydroxybenzophenone or di p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene Base-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methyl phenylbenzothiazoline, 2-(4-bibenzoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazole phenoline, 2-(4-bibenzoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazole phenoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline , 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-bibenzoylmethylene)-3-methylbenzoxazoline, 2-(β -Naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-bibenzoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m-nitroaniline or p-nitroaniline, 2,4,6-trinitroaniline phenylaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthaloketone, Acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol and 9-anthracenecarboxylic acid), benzopyridine Fran, azo indolizine, melocoumarin, etc.

Preferred are aromatic-2-hydroxyketones (benzophenones), coumarins, coumarinones, carbonyl dicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and Acetophenone 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, dielectrics and conductive substances can be added in order to change the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film. When forming a liquid crystal aligning film, the hardness and density of a film are improved, and a crosslinkable compound is added.

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 the substrate with the conductive film for driving the transverse electric field, it can be heated at 50-200° C., preferably at 50-150° C. The solvent was evaporated 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 step [I] and before the next step [II], 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 point. 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 a temperature range at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expression temperature). In the case of a film surface such as a coating film, it is expected that the liquid crystallinity expression temperature of the coating film surface is lower than the liquid crystallinity expression temperature when the photosensitive side chain type polymer that can express liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystallinity expression temperature of the coating film surface. That is, the temperature range of the heating temperature after the irradiation of polarized ultraviolet rays is preferably: the lower limit is 10°C lower than the lower limit of the temperature range of the liquid crystallinity expression temperature of the side chain type polymer used, and the lower limit is lower than the temperature range of the liquid crystal temperature range. A temperature 10° C. lower than the upper limit 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. In this case, it may be difficult to reorient in one direction by self-assembly.

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

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 [IV]>

The step [IV] is to prepare the substrate (first substrate) having a liquid crystal alignment film on the conductive film for driving a transverse electric field obtained in [III] with the substrate (first substrate) obtained in the above [I'] to [III'] similarly without The substrate (second substrate) with the liquid crystal aligning film of the conductive film is arranged oppositely with the liquid crystal aligning films of the two facing each other, and a liquid crystal cell is produced by a known method, thereby producing a transverse electric field drive type liquid crystal display element. process. It should be noted that, in the steps [I'] to [III'], except that in the step [I], a substrate without a conductive film for driving a transverse electric field is used instead of a substrate having a conductive film for driving a transverse electric field, It can carry out similarly to process [I]-[III]. The difference between steps [I]-[III] and steps [I']-[III'] lies in the presence or absence of the above-mentioned conductive film, so the description of steps [I']-[III'] 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 photofries rearrangement group or a An embodiment of a side-chain polymer having a structure in which an isomerized group is a photoreactive group will be described as a second embodiment.

Fig. 1 schematically illustrates the isotropic phase in the method for producing a liquid crystal aligning film using a side chain type polymer having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. A diagram of an example of heterosexual introduction processing. Fig. 1(a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 1(b) is a diagram schematically showing the side chain type polymer film after polarized light irradiation State diagram, Fig. 1 (c) is a diagram schematically showing the state of the side chain type polymer film after heating, especially when the introduced anisotropy is small, that is, in the first embodiment 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 15% of the ultraviolet irradiation dose for maximizing ΔA.

Fig. 2 schematically illustrates the isotropic orientation in the method for producing a liquid crystal aligning film using a side chain type polymer having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. A diagram of an example of heterosexual introduction processing. Fig. 2 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 2 (b) is a diagram schematically showing the side chain type polymer film after polarized light irradiation State diagram, Fig. 2(c) is a diagram schematically showing 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 of the side chain type polymer. Fig. 3 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 3 (b) is a diagram schematically showing the side chain type polymer film after polarized light irradiation State diagram, Fig. 3 (c) is a diagram schematically showing the state of the side chain type polymer film after heating, especially when 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.

4 is a diagram schematically illustrating a side-chain type polymer having a structure having a photo-Friesian rearrangement group represented by the above-mentioned formula (19) as a photoreactive group in a second embodiment of the present invention, It is a figure of an example of the anisotropy introduction process in the manufacturing method of a liquid crystal aligning film. Fig. 4 (a) is a diagram schematically showing the state of the side chain type polymer film before polarized light irradiation, and Fig. 4 (b) is a diagram schematically showing the side chain type polymer film after polarized light irradiation State diagram, Fig. 4 (c) is a diagram schematically showing 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, in the treatment of 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, A coating film 1 is formed on a 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, in the treatment of 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, 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, in the treatment of 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 amount in the [II] step is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, a 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, in the process of introducing anisotropy to the coating film, a liquid crystal using a side chain type polymer having the structure of the photo-Fries rearrangement group represented by the above formula (19) is applied. In the case of an alignment film, 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 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 in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, 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 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 isotropic coating film 3 is irradiated with polarized ultraviolet rays. 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, [II] When the ultraviolet irradiation amount in the step is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Thus, as shown in (b) of FIG. 3 , among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6 a having a photosensitive group preferentially generates light. Fries rearrangement and other photoreactions. 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 form 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 in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, 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, and self-assembly occurs along the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side containing the mesogen component Chain 2 undergoes 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 in 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 undergo reorientation. 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 amount in the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount that makes ΔA the maximum, the coating film 5 after polarized light irradiation 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 the spontaneous generation occurs in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays. Assembled, the side chains 6 including the mesogen component are re-aligned. 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 in 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 generated, it occurs in a direction parallel to the polarization direction of the irradiated ultraviolet rays. As a result of self-assembly, 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, the coating film used for the method of this invention can be made into the liquid crystal aligning film excellent in orientation control ability by efficiently introducing anisotropy by irradiating the coating film with polarized ultraviolet rays and heat processing sequentially.

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. In this case, 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 self-assembly by heating. advance.

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 anisotropy in the film can be efficiently formed.

In the coating film used in the method of the present invention, optimize the photocrosslinking reaction, photoisomerization reaction or photophoretic reaction of the photosensitive group in the side chain of the side chain type polymer film by optimizing the irradiation amount of polarized ultraviolet rays. The amount of the Lys 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 determined 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 50% of the amount of polarized ultraviolet rays that realize ΔAmax. %In the 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 realizes ΔAmax corresponds to the entire photosensitive group that the side chain type polymer film has. 0.1 mol% to 20 mol% of the amount of polarized ultraviolet rays that undergo photocrosslinking reactions.

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 described above, the substrate for a transverse electric field driven liquid crystal display element manufactured by the composition of the present invention and the method using the same or a transverse electric field driven liquid crystal display element having the substrate has excellent reliability and can be suitably used in large Picture and high-definition LCD TV, etc.

Example

Hereinafter, although an Example is used and this invention is demonstrated, this invention is not limited to this Example.

The analysis apparatus and analysis conditions used for the synthesis of the specific glycidyl compound of this invention are shown below.

(measurement of ¹ H-NMR)

Device: Varian NMR System 400NB (400MHz) (manufactured by Varian)

Determination solvent: CDCl ₃ (deuterated chloroform), DMSO-d ₆ (deuterated dimethyl sulfoxide)

Reference substances: TMS (tetramethylsilane) (δ: 0.0ppm, ¹ H), CDCl ₃ (δ: 77.0ppm, ¹³ C)

Abbreviations used in Examples are as follows.

<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).

<Hydroxyalkyl compound>

T1: Primid XL-552: (N,N,N',N'-tetrakis-(2-hydroxyethyl)adipamide)

T2: Primid SF-4510

For T1 and T2, commercially available compounds were used.

<Comparative example>

X1: Tetraglycidyl diaminodiphenylmethane (YH-434L)

X1 uses a commercially available product.

<Organic solvent>

THF: Tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

<polymerization initiator>

AIBN: 2,2'-azobisisobutyronitrile

<Polymerization Example 1: Polymethacrylic acid>

MA1 (13.3 g, 40.0 mmol) and MA2 (18.4 g, 60.0 mmol) were dissolved in THF (182.3 g), and after degassing with a diaphragm pump, AIBN (0.82 g, 5.0 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of the methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This deposit was wash|cleaned with diethyl ether, and it dried under reduced pressure in the oven of 40 degreeC, and obtained the methacrylate polymer powder.

54.0 g of NMP was added to 6.0 g of the obtained powder, and it stirred at room temperature for 3 hours. A methacrylate polymer solution (M1) having a solid content concentration of 10.0% by weight was obtained. The polymer was completely dissolved at the end of stirring.

<Polymerization Example 2: Polymethacrylic acid>

MA1 (6.64 g, 20.0 mmol) and MA2 (24.5 g, 80.0 mmol) were dissolved in THF (181.2 g), and after degassing with a diaphragm pump, AIBN (0.82 g, 5.0 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of the methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This deposit was wash|cleaned with diethyl ether, and it dried under reduced pressure in the oven of 40 degreeC, and obtained the methacrylate polymer powder.

54.0 g of NMP was added to 6.0 g of the obtained powder, and it stirred at room temperature for 3 hours. A methacrylate polymer solution (M2) having a solid content concentration of 10.0% by weight was obtained. The polymer was completely dissolved at the end of stirring.

<Synthesis Example 1>

Synthesis of Specific Hydroxyalkyl Compounds (T3)

To an acetonitrile solution (125 g) of piperazine (25.0 g, 300 mmol), methyl acrylate (56.8 g, 660 mmol) was added dropwise over 1 hour, followed by stirring at room temperature for 2 hours. Thereafter, the resulting solution was concentrated to obtain T3-1 as a colorless oil. (yield: 77.8g, yield: 100%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 3.58 (6H, s), 2.54-2.50 (4H, m), 2.46-2.33 (4H, m), 32.33 (8H, br).

A DMF solution (129 g) added with T3-1 (12.9 g, 50 mmol), diethanolamine (11.0 g, 105 mmol), sodium ethoxide (0.34 g, 5 mmol) was stirred at room temperature for 18 hours. Thereafter, the precipitated white solid was collected by filtration, and recrystallized with methanol (130 g), whereby T3 was obtained. (yield: 11.6g, yield: 57.3%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 4.84-4.82 (2H, t), 4.66-4.64 (2H, t), 3.53-3.30 (16H, m), 2.49 (8H, br), 2.36 (8H,br).

<Synthesis Example 2>

Synthesis of Specific Hydroxyalkyl Compounds (T4)

To an acetonitrile solution (31.5 g) of 1,3-di-4-piperazinylpropane (6.31 g, 30 mmol), methyl acrylate (5.68 g, 66 mmol) was added dropwise over 1 hour, followed by stirring at room temperature for 2 hours. Thereafter, the resulting solution was concentrated to obtain T4-1 as a colorless oil. (yield: 11.5g, yield: 100%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 3.68 (6H, s), 2.86 (4H, d), 2.67 (4H, t), 2.52 (4H, t), 1.96-1.92 (4H, m ),1.66-1.64(4H,m),1.27(2H,br),1.12(10H,br).

An ethanol solution (57.3 g) added with T4-1 (11.5 g, 30 mmol), diethanolamine (9.46 g, 90 mmol), and sodium ethoxide (0.20 g, 3 mmol) was stirred at room temperature for 18 hours. Thereafter, concentration was carried out, and the resulting solid was recrystallized from IPA (76.4 g), whereby T4 was obtained. (yield: 5.60g, yield: 35.5%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 4.86 (2H, br), 4.67 (2H, br), 3.50-3.30 (16H, m), 2.82-2.78 (4H, m), 2.55-2.47 (8H,m),1.87-1.81(4H,m),1.60-1.57(4H,m),1.25-1.03(12H,m).

<Synthesis Example 3>

Synthesis of Specific Hydroxyalkyl Compounds (T5)

In a DMF solution (39.3 g) of diethanolamine (15.8 g, 150 mmol), dicyclohexylmethane-4,4'-diisocyanate (11.5 g, 30 mmol) was added dropwise at room temperature for 1 hour, and stirred at room temperature for 18 Hour. THF (120 g) was added to the obtained solution, and after stirring at room temperature for 2 hours, the precipitated white solid was recovered by filtration to obtain T5. (yield: 10.8g, yield: 45.7%)

¹ H-NMR (400MHz, DMSO-d, δppm): 6.43(2H,d), 6.05(2H,d), 5.04(2H,br), 4.88-4.86(2H,t), 3.63(1H,br) ,3.51-3.44(8H,m),3.34-3.24(9H,m),1.78-1.65(4H,m),1.51-1.41(6H,m),1.19-1.03(8H,m).0.92-0.83( 2H,m).

<Synthesis Example 4>

Synthesis of Specific Hydroxyalkyl Compounds (T6)

In the acetonitrile solution (25.2g) of 4,4'-bipiperidine (5.05g, 30mmol), methyl acrylate (5.68g, 66mmol) was added dropwise over 1 hour, and after stirring at room temperature for 2 hours, the resulting solution was Concentration was carried out, whereby T6-1 was obtained as a colorless oil. (yield: 10.3g, yield: 99.9%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 3.68 (6H, s), 2.93-2.89 (4H, m), 2.69-265 (4H, m), 2.55-2.50 (4H, t), 1.96 -1.89(4H,m),1.69-1.66(4H,m),1.30-1.23(4H,m),1.09-0.99(2H,m).

An ethanol solution (51.0 g) added with T6-1 (10.2 g, 30 mmol), diethanolamine (9.46 g, 90 mmol), and sodium ethoxide (0.20 g, 3 mmol) was stirred at room temperature for 18 hours. Thereafter, concentration was carried out, and the resulting solid was recrystallized from IPA (60.5 g), whereby T6 was obtained. (yield: 4.92g, yield: 33.7%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 4.83 (2H, br), 4.66-4.33 (2H, t), 3.50-3.29 (16H, m), 2.86-2.83 (4H, m), 2.51 -2.41(8H,m),1.83-1.78(4H,m),1.61-1.58(4H,m),1.18-0.94(6H,m).

<Synthesis Example 5>

Synthesis of Specific Hydroxyalkyl Compounds (T7)

To a methanol solution (263 g) of diethanolamine (52.6 g, 500 mmol), methyl acrylate (56.0 g, 650 mmol) was added dropwise over 1 hour, followed by stirring at room temperature for 2 hours. Thereafter, the resulting solution was concentrated, whereby T7-1 was obtained as a colorless oil. (yield: 99.7g, yield: 95.9%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 4.26 (2H, t), 3.54 (3H, s), 3.37-3.33 (4H, m), 2.73-2.70 (2H, m), 2.46 (4H ,t),2.38(2H,t).

The ethanol solution (43.1 g) added with T7-1 (22.9 g, 120 mmol), piperazine (4.31 g, 50 mmol), sodium ethoxide (0.34 g, 5 mmol) was stirred under reflux for 18 hours. Thereafter, concentration was carried out, and T7 was obtained by reslurry-purifying the obtained solid with IPA (86.2 g). (yield: 6.46g, yield: 31.9%)

¹ H-NMR (400MHz, DMSO-d ₆ , δppm): 4.70(4H,br), 3.52-3.29(16H,m), 2.56-2.25(4H,m), 2.50(8H,br), 2.27(8H ,br).

<Example 1>

33.33 g of BCS and 0.15 g of T1 were added to 50.0 g of methacrylic polymer solution M1 obtained in polymerization example 1, and it stirred at room temperature for 3 hours, and obtained liquid crystal aligning agent AL1.

<Examples 2 to 19>

Except having used the composition shown in Table 1, liquid crystal aligning agents AL2-AL19 of Examples 2-19 were obtained by the method similar to Example 1, and the liquid crystal cell was produced using this. In addition, the voltage holding ratio (VHR) and afterimage characteristics were measured by the same method as in Example 1. The results are also shown in Table 1.

<Comparative Examples 1 to 3 (Controls 1 to 3)>

Using the polymer solutions (M1, M2) obtained in Polymerization Examples 1 and 2, a liquid crystal cell was prepared in the same manner as when using the above-mentioned liquid crystal aligning agent (AL1), and VHR and afterimage characteristics were evaluated by the same method.

[Production of liquid crystal unit]

Using the liquid crystal aligning agent (AL1) obtained above, preparation of the liquid crystal cell was performed in accordance with 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.

In addition, each pixel is divided up and down with a curved portion at the center thereof, 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 (AL1) obtained above 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 ultraviolet rays of 313 nm at 15 mJ/cm ² through a polarizing plate, it was heated on a 150° C. hot plate for 10 minutes to obtain a substrate with a liquid crystal aligning film.

In addition, as a counter substrate, a coating film was similarly formed on a glass substrate having no electrodes and a columnar spacer having a height of 4 μm, 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 might face|face and the orientation direction becomes 0 degree|times, the sealant was heat-cured, 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 configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

Also about the liquid crystal aligning agent (AL2-AL9) obtained in Examples 2-19, the liquid crystal cell was produced by the method similar to AL1.

(orientation observation)

A liquid crystal cell was produced by the method described above. Thereafter, reorientation treatment was performed for 60 minutes in an oven at 120°C. Thereafter, observation was performed with a polarizing microscope in which a polarizing plate was in a crossed Nichol prism state.

When the liquid crystal cell was rotated to display a black state, the state in which there were no bright spots and poor orientation was rated as good. As a result of observing orientation, all Examples and comparative examples (comparisons 1, 2, and 3) showed favorable liquid-crystal orientation.

(Voltage retention rate (VHR) evaluation)

Using the liquid crystal cell produced above, an AC voltage of 16 Vpp was applied at a frequency of 30 Hz for 168 hours in a constant temperature environment of 70°C. Thereafter, between the pixel electrode and the counter electrode of the liquid crystal cell was short-circuited, and this state was left to stand at room temperature for 1 hour. A voltage of 1 V was applied to the obtained cell at a temperature of 70° C. for 60 μs, the voltage after 16.67 ms was measured, and the extent to which the voltage could be maintained was calculated as a voltage retention ratio (VHR). In addition, VHR in a constant temperature environment of 70° C. was calculated, and VHR (initial stage)-VHR (after aging) was calculated and shown in Table 1 below as ΔVHR. In addition, the measurement of the voltage retention ratio used the voltage retention ratio measurement apparatus VHR-1 manufactured by TOYO Corporation.

The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, compared with the comparative example based on the embodiment of the present invention which is the same as (A) component but does not contain (B) component, in more detail, Example 1, 3, 10, 12, 14, 16 is compared with Control 1, and Examples 4 to 9 are compared with Control 2. It can be seen that the ΔVHR value of the Examples is small, and thus the voltage retention ratio (VHR) does not decrease due to heat aging.

A liquid crystal cell was produced by the same method except having fired at the firing temperature of 100 degreeC and 150 degreeC among the said liquid crystal cell manufacturing methods.

[Table 2]

As shown in Table 2, it can be seen that the initial value of the voltage retention ratio (VHR) is improved compared with the comparative examples (comparisons 1 and 3) by including the (B) component in the examples based on the present invention, and the firing temperature caused There is little variation in voltage retention (VHR), and good voltage retention can be obtained at a low firing temperature.

<Evaluation of afterimage>

The liquid crystal cell for the IPS mode prepared in Example 1 was placed between two polarizing plates arranged so that the polarization axis was perpendicular, and the backlight was turned on in advance with no voltage applied, and the arrangement angle of the liquid crystal cell was adjusted to Minimize the brightness of the transmitted light. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the pixel becomes darkest to the angle at which the first region becomes darkest is calculated as the initial orientation azimuth angle. Next, in an oven at 70° C., an AC voltage of 16 V _PP was applied at a frequency of 30 Hz for 168 hours. Thereafter, between the pixel electrode and the counter electrode of the liquid crystal cell was short-circuited, and this state was left to stand at room temperature for 1 hour. After standing, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuth before and after AC driving was calculated as an angle Δ (deg.). Other examples were also measured in the same manner. As a result, the angle Δ was 0.1 or less in all the examples.

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 (21)

1. A composition comprising: (A) A photosensitive side chain type polymer that exhibits liquid crystallinity in a specific temperature range, (B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and (C) Organic solvents. 2. The composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofries rearrangement. 3. The composition according to claim 1 or 2, wherein the compound having 2 to 6 nitrogen atoms bonded with at least one hydroxyalkyl group in a molecule of the component (B) is represented by the following formula (b )express, In formula (b), R ¹ is an organic group with n valence, L ¹ represents a single bond, an alkylene group with 1 to 10 carbons or NX ¹ ; X ¹ represents a hydrogen atom or an alkyl group, in addition, X ¹ optionally forms an alkylene group together with other X ¹ , and X ¹ optionally passes Bonding with R1 to form ^a ring structure; L ² represents a single bond or an alkylene group with 1 to 10 carbons; L ³ represents a single bond, NH or N-alkyl; L ⁴ represents a single bond or an alkylene group with 1 to 10 carbons; L ⁵ represents a single bond or carbonyl, and when L ³ is NH or N-alkyl, L ⁴ and L ⁵ are different and represent a single bond; L ⁶ and L ⁷ each independently represent a linear or branched alkylene group with 2 to 20 carbons; The alkylene groups in L ¹ , L ² , L ⁴ , L ⁶ and L ⁷ are optionally substituted with one or more substituents selected from halogen and hydroxyl, which may be the same or different; and n is an integer of 2-6. 4. The composition according to claim 3, wherein n is 2 or 3. 5. The composition according to claim 3 or 4, wherein at least one of L ⁶ and L ⁷ is represented by the following formula (b1), In formula (b1), R ² to R ⁵ each independently represent any of a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group. 6. The composition according to any one of claims 3 to 5, wherein L ⁶ and L ⁷ in formula (b) both represent ethylene groups. 7. The composition according to any one of claims 3 to ⁶ , wherein, in R or L ^of formula (b), the atom directly bonded to the carbonyl group of formula (b) does not form an aromatic ring carbon atom. 8. The composition according to any one of claims 3 to 7, wherein R in formula (b) is ^a structure selected from following b2-1 to b2-29, 9. The composition according to any one of claims 1 to 8, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6), In formulas (1) to (6), 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 of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, wherein R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; _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 The alkyloxy 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 is 2, X can be 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 1-5 carbons or alkyloxy group with 1-5 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 ; Wherein, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, the P or Q on the side where -CH=CH- is bonded is an aromatic ring, and the number of P is 2 In the case of the above, P may be the same or different from each other, and when the number of Q is 2 or more, the Q may be 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. 10. The composition according to any one of claims 1 to 8, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10), In formulas (7) to (10), A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, - CH=CH-CO-O- or -O-CO-CH=CH-; Y 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 of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, wherein R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; 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 is 2, X can be the same or different from each other; l represents an integer from 1 to 12; m represents an integer from 0 to 2, 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; _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 The alkyloxy substitution; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as _Y1 . 11. The composition according to any one of claims 1 to 8, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13), In formulas (11) to (13), A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH- CO-O- or -O-CO-CH=CH-; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X is 2, X can be the same or different from each other; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m2 represents an integer from 1 to 3; R 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 A group in which 2 to 6 rings are bonded via a bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN) _2. -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, or a hydroxyl group or an alkoxy group with 1 to 6 carbons, wherein, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbons. 12. The composition according to any one of claims 1 to 8, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15), In formula (14) or (15), A each independently represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH- CO-O- or -O-CO-CH=CH-; Y 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 of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, wherein R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; 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 is 2, X can be the same or different from each other; l represents an integer of 1-12; m1 and m2 represent an integer of 1-3. 13. The composition according to any one of claims 1 to 8, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17), In formula (16) or (17), A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -or-O-CO-CH=CH-; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH- , when the number of X is 2, X can be the same or different from each other; l represents an integer of 1-12; m represents an integer of 0-2. 14. The composition according to any one of claims 1 to 8, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formula (18) or (19), In formula (18) or (19), A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH= CH-CO-O- or -O-CO-CH=CH-; 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 of the above group by means of the bonding group B, the hydrogen atoms bonded to them are each independently optionally replaced by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, wherein R ₀ represents a hydrogen atom or an alkane with 1 to 5 carbons base; One of q1 and q2 is 1 and the other is 0; l represents an integer from 1 to 12; m1 and m2 represent an integer from 1 to 3; 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 alkyl group with 1 to 5 carbons Oxygen. 15. The composition according to any one of claims 1 to 8, wherein the component (A) has a photosensitive side chain represented by the following formula (20), In formula (20), A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O -CO-CH=CH-; 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 A group formed by bonding 2 to 6 rings via a bonding group B, the hydrogen atoms bonded to them are each independently represented by -COOR ₀ , -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons or an alkyloxy group with 1 to 5 carbons, in the formula, R ₀ represents a hydrogen atom or an alkyl group with 1 to 5 carbons ; 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 is 2, X can be the same or different from each other; l represents an integer of 1-12, and m represents an integer of 0-2. 16. The composition according to any one of claims 1 to 15, wherein the component (A) has any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31), In formulas (21) to (31), A and B have the same definitions 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 alkyloxy 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; One of q1 and q2 is 1 and the other is 0; l represents an integer from 1 to 12; m represents an integer from 0 to 2, wherein, in formulas (23) to (24), the sum of all m is more than 2, and in formulas (25) to (26), the sum of all m 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 carbon atoms, and Alkyl or alkyloxy; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -. 17. A method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field-driven type liquid crystal display element, which obtains the liquid crystal alignment film endowed with orientation control capability by possessing the following steps: [1] The composition described in any one of claims 1 to 16 is coated on a substrate having a transverse electric field driving conductive film to form a coating film; [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]. 18. A substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, manufactured by the method according to claim 17. 19. A lateral electric field driven liquid crystal display element comprising the substrate according to claim 18. 20. 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 according to claim 18, that is, the first substrate; The process of obtaining the second substrate having the following liquid crystal aligning film, which is provided with the following steps [I'], [II'] and [III'] to obtain a liquid crystal aligning film endowed with orientation control ability; and [IV] The process of arranging the first substrate and the second substrate facing each other in such a manner 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 that exhibits liquid crystallinity in a specific temperature range; molecule, (B) a compound having 2 to 6 nitrogen atoms bonded to at least one hydroxyalkyl group in one molecule, and (C) 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']. 21. A transverse electric field driven liquid crystal display element manufactured by the method according to claim 20.