JP6932335B2 - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and new monomer - Google Patents

Description

In the present invention, a novel polymer having a specific structural unit, a composition containing the polymer (liquid crystal alignment agent), a liquid crystal alignment film for a transverse electric field driven liquid crystal display element using the same, and a substrate having the alignment film. Regarding the manufacturing method of.

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices, and have made remarkable progress in recent years, such as being used in large-scale television applications. The liquid crystal display element is configured by sandwiching the liquid crystal layer between, for example, a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired orientation state between the substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, is formed on the surface of the substrate that sandwiches the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to have a role of controlling the pretilt angle of the liquid crystal in addition to the role of orienting the liquid crystal in a certain direction such as a direction parallel to the substrate. The ability to control the orientation of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as the orientation control ability) is given by performing an orientation treatment on the organic film constituting the liquid crystal alignment film.

A rubbing method has been conventionally known as an orientation treatment method for a liquid crystal alignment film for imparting an orientation control ability. The rubbing method is to rub the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing) in a rubbing direction (rubbing direction). This is a method of orienting a liquid crystal display. Since this rubbing method can easily realize a relatively stable orientation state of a liquid crystal display, it has been used in a conventional manufacturing process of a liquid crystal display element. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance and electrical characteristics has been mainly selected.

However, the rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like may cause problems such as dust generation and generation of static electricity. In addition, due to the recent high definition of the liquid crystal surface element and the unevenness of the corresponding electrode on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth, and is uniform. In some cases, the orientation of the liquid crystal could not be achieved.

Therefore, the photo-alignment method has been actively studied as another alignment treatment method for the liquid crystal alignment film without rubbing.

There are various photo-alignment methods, but anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is oriented according to the anisotropy.

As the main photo-orientation method, a decomposition type photo-orientation method is known. In this method, for example, the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide left without decomposition (see, for example, Patent Document 1).

Further, as another photo-orientation method, a photocrosslinking type or a photoisomerization type photo-alignment method is also known. In the photocrosslinking type photoalignment method, for example, polyvinyl synnamate is used to irradiate polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at a double bond portion of two side chains parallel to polarized light. Then, the liquid crystal is oriented in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In the photoisomerization type photoorientation method, when a side chain type polymer having azobenzene in the side chain is used, it is irradiated with polarized ultraviolet rays to cause an isomerization reaction in the azobenzene part of the side chain parallel to polarized light, resulting in polarization. The liquid crystal is oriented in a direction orthogonal to the direction (see, for example, Non-Patent Document 2).

As described in the above example, the method of aligning the liquid crystal alignment film by the photoalignment method does not require rubbing, and there is no concern about dust generation or static electricity generation. Then, the orientation treatment can be applied to the substrate of the liquid crystal display element having an uneven surface, which is a method of orientation treatment of the liquid crystal alignment film suitable for an industrial production process.

Further, as a photo-oriented polymer, a liquid crystal aligning agent using a photo-reactive polymer that exhibits liquid crystallinity in a predetermined temperature range has also been proposed.

Japanese Patent No. 3893659 International Patent Application Publication WO2014 / 054785 Pamphlet

M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992). K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

However, when a photoreactive polymer that exhibits liquid crystallinity in a predetermined temperature range is used as the photo-oriented polymer, the solubility may decrease depending on the structure of the polymer, which may not be practical. Therefore, there is a demand for a highly soluble polymer while introducing a wide variety of structures.

The present inventors have found that the solubility of a polymer can be improved by introducing a specific structural unit into a photo-oriented polymer. That is, an object of the present invention is to provide a photoreactive polymer introduced with a specific structural unit capable of improving the solubility of the polymer, and a liquid crystal alignment agent containing the same. It also provides new monomers for introducing the particular structural unit.

As a result of diligent studies to achieve the above problems, the present inventors have found the following inventions.

<1> In the polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent, the resin as the component (A) is as follows. A polymer composition comprising a side chain represented by the formula (a). In particular, a polymer composition for producing a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element.
In formula (a), L is a linear or branched alkylene having 1 to 16 carbon atoms.
X represents CH _{2 -CH 2} , CH = CH or C≡C.
Y ¹ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a dialkylamino group. (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. or branched-chain acyl group, a carboxyl group, a Y ¹ -6 from a good formula Y ¹ -1 be substituted with a substituent selected from an aldehyde group and a nitro group (** represents a bonding position to X , *** represents the position of connection with ^{Y 2).}
Y ² represents -COOH, -CR ³ = CR ^4- COOH, -CR ⁵ = CR ^6- CO-O-Y ³ or -O-CO-CR ⁵ = CR ^6- Y ³ .
R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively.
R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively.
Y ³ are each independently a halogen group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. Alternatively, a phenyl group, a biphenyl group, a naphthyl group, an alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl- which may be substituted with a substituent selected from an acyl group, a carboxyl group, an aldehyde group and a nitro group of the branched chain. Represents a cyclohexyl group or a cyclohexyl-phenyl group.

<2> In the above <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries rearrangement.
<3> In the above <1> or <2>, the component (A) preferably has any one of the photosensitive side chains selected from the group consisting of the following formulas (1) to (6).

In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-. Represents O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, 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. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

<4> In any of the above <1> to <3>, the component (A) has any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31). good.
In the formula, A and B have the same definition as above;
Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and, with a group selected from the group consisting of Yes, the hydrogen atoms attached to them may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ contains 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, and nitrogen. Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the sum of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon with 5 to 8 carbon atoms, alkyl. Represents a group or alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<5> [I] A step of applying any of the above compositions <1> to <4> on a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
A method for manufacturing a substrate having the liquid crystal alignment film, which obtains a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which the orientation control ability is imparted.
<6> A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method of <5> above.
<7> A transverse electric field-driven liquid crystal display element having the substrate of <6> above.

<8> Step of preparing the substrate (first substrate) of <6>above;
[I'] A step of applying the polymer composition of any of the above <1> to <17> on the second substrate to form a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III'] [II'];
A step of obtaining a liquid crystal alignment film having an orientation control ability by having the liquid crystal alignment film, and obtaining a second substrate having the liquid crystal alignment film; and [IV] Liquid crystal alignment films of the first and second substrates via the liquid crystal. A step of arranging the first and second substrates so as to face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which obtains a horizontal electric field drive type liquid crystal display element.
<9> A transverse electric field drive type liquid crystal display element manufactured by the above <8>.

<10> A compound represented by the following formula (am1).
In the formula (am1), PL is a polymerizable group and represents a polymerizable group selected from the group consisting of the following formulas PL-1 to PL-5. In the formula PL-1~PL-5, ^{R 1} and ^R 2, ^{R 3} is a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, or has been in the 1 to 10 carbon atoms substituted by halogen It represents a linear or branched alkyl group (* represents the bonding position with L).
L is a linear or branched alkylene having 1 to 16 carbon atoms.
X represents CH _{2 -CH 2} , CH = CH or C≡C.
Y ¹ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a dialkylamino group. (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. or branched-chain acyl group, a carboxyl group, a Y ¹ -6 from a good formula Y ¹ -1 be substituted with a substituent selected from an aldehyde group and a nitro group (** represents a bonding position to X , *** represents the coupling position with ^{Y 2.).}
Y ² represents -COOH, -CR ³ = CR ^4- COOH, -CR ⁵ = CR ^6- CO-O-Y ³ or -O-CO-CR ⁵ = CR ^6- Y ³ .
R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively.
R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively.
Y ³ are each independently a halogen group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. Alternatively, a phenyl group, a biphenyl group, a naphthyl group, an alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl- which may be substituted with a substituent selected from an acyl group, a carboxyl group, an aldehyde group and a nitro group of the branched chain. Represents a cyclohexyl group or a cyclohexyl-phenyl group.

According to the present invention, a polymer having a specific structural unit can be obtained, and the obtained polymer has improved solubility as compared with a conventional polymer. As a result, in order to realize various characteristics required for the liquid crystal display element, when introducing the structural unit, it becomes possible to introduce the structural unit without worrying about the decrease in the solubility of the polymer. As a result, it is possible to provide a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element and a transverse electric field driven liquid crystal display element having the substrate, which are provided with high efficiency orientation control ability and excellent seizure characteristics. can.

As a result of diligent research, the present inventor has obtained the following findings and has completed the present invention.
The polymer composition of the present invention has a photosensitive side-chain polymer capable of exhibiting liquidity (hereinafter, also simply referred to as a side-chain polymer), and can be obtained by using the polymer composition. The coating film to be obtained is a film having a photosensitive side chain polymer capable of exhibiting liquidity. This coating film is subjected to an orientation treatment by polarized light irradiation without performing a rubbing treatment. Then, after the polarization irradiation, the side chain type polymer film is heated to obtain a coating film having an orientation control ability (hereinafter, also referred to as a liquid crystal alignment film). At this time, the slight anisotropy developed by the polarization irradiation becomes the driving force, and the liquid crystal side chain polymer itself is efficiently reoriented by self-assembly. As a result, highly efficient alignment processing can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high orientation control ability can be obtained.

Further, in the polymer composition of the present invention, the side chain type polymer which is the component (A) contains the side chain represented by the above formula (a). As a result, the solubility of the polymer composition in the organic solvent becomes good. This phenomenon is caused by the fact that the polymer represented by the above formula (a) has a weaker interaction between the polymers due to the effect of the linking group than the polymer having a similar structure having different linking groups, and dramatically enhances the desired effect. I thought there was. It should be noted that these include the inventor's views on the mechanism of the present invention and are not binding on the present invention.

Further, in the polymer composition of the present invention, in addition to the side chain type polymer which is the component (A) and the organic solvent which is the component (B), a tetracarboxylic acid derivative and a diamine compound are used as the component (C). Polyamic acid produced by polymerization reaction, or polyimide produced by imidizing polyamic acid, polyurea produced by polymerizing a diisocyanate compound and a diamine compound, and a diisocyanate compound and a tetracarboxylic acid derivative. It is also possible to contain a polyurea polyamic acid produced by polymerizing a diamine compound and a polyurea polyimide produced by imidizing the polyurea polyamic acid.
Hereinafter, embodiments of the present invention will be described in detail.

<Polymer composition>
The polymer composition is applied onto a substrate having a conductive film for driving a transverse electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention is
In a polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent, the resin that is the component (A) is the following formula (a). It is characterized by containing a side chain represented by.

<< (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range.
The side chain polymer (A) preferably 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.
The side chain polymer (A) preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The side chain type polymer (A) preferably has a mesogen group because it exhibits liquid crystallinity in a temperature range of 100 ° C. to 300 ° C.

In the side chain type polymer (A), a side chain having photosensitivity is bonded to the main chain, and a cross-linking reaction, an isomerization reaction, or a photo Fries rearrangement can occur in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a cross-linking reaction or a photo-Fries rearrangement in response to light is desirable, and one that causes a cross-linking reaction is more desirable. In this case, even if it is exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogen component. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.

The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and the side chain contains a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip. It has a structure having a photosensitive group bonded to a portion and undergoing a cross-linking reaction or an isomerization reaction in response to light, a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogen component. The structure can have a phenylbenzoate group that undergoes a photofreeze rearrangement reaction.

More specific examples of the structure of the photosensitive side chain polymer capable of exhibiting liquidity include (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and the like. The structure has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6). Is preferable.

In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-. Represents O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, 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. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

The side chain is preferably any one of the photosensitive side chains 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 definition as above;
l represents an integer from 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer from 0 to 12 (where B is a single bond when n = 0).

The side chain is preferably any one of the photosensitive side chains 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 is preferably 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 is preferably 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.

The side chain is preferably 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 is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl having 1 to 5 carbon atoms. Represents an oxy group.

The side chain is preferably 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.

Further, the side chain type polymer (A) contains a side chain represented by the following formula (a).
In formula (a), L is a linear or branched alkylene having 1 to 16 carbon atoms.
X represents CH _{2 -CH 2} , CH = CH or C≡C.
Y ¹ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a dialkylamino group. (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. or branched-chain acyl group, a carboxyl group, a Y ¹ -6 from a good formula Y ¹ -1 be substituted with a substituent selected from an aldehyde group and a nitro group (** represents a bonding position to X , *** represents the coupling position with ^{Y 2.).}

Y ² represents -COOH, -CR ³ = CR ^4- COOH, -CR ⁵ = CR ^6- CO-O-Y ³ or -O-CO-CR ⁵ = CR ^6- Y ³ .
R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively.
R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively.
Y ³ are each independently a halogen group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. Alternatively, a phenyl group, a biphenyl group, a naphthyl group, an alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl- which may be substituted with a substituent selected from an acyl group, a carboxyl group, an aldehyde group and a nitro group of the branched chain. Represents a cyclohexyl group or a cyclohexyl-phenyl group.

Further, the side chain type polymer (A) preferably has any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).
In the formula, A, B, q1 and q2 have the same definitions as above;
Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and, with a group selected from the group consisting of Yes, the hydrogen atoms attached to them may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ contains 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, and nitrogen. Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the sum of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon with 5 to 8 carbon atoms, alkyl. Represents a group or alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<< Manufacturing method of photosensitive side chain polymer >>
The photosensitive side chain polymer capable of exhibiting the liquidity can be obtained by polymerizing the photoreactive side chain monomer having the photosensitive side chain and the liquid crystal side chain monomer.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.
As the photoreactive group of the side chain, the following structure and its derivative are preferable.

More specific examples of photoreactive side chain monomers include from radically polymerizable groups such as (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. A polymerizable group composed of at least one selected from the above group and a photosensitive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formulas (7) to (6). A photosensitive side chain consisting of at least one of the above formulas (11) to (13), a photosensitive side chain consisting of at least one of the above formulas (14) or (15), and a photosensitive side chain represented by the above formula (14) or (15). , The photosensitive side chain represented by the above formula (16) or (17), the photosensitive side chain represented by the above formula (18) or (19), and the photosensitive side chain represented by the above formula (20). It is preferable that the structure has.

[Monomer having a structural unit represented by the formula (a)]
Examples of the monomer having a structural unit represented by the formula (a) include a compound represented by the following formula (am1).
In the formula (am1), PL is a polymerizable group and represents a polymerizable group selected from the group consisting of the following formulas PL-1 to PL-5. In the formula PL-1~PL-5, ^{R 1} and ^R 2, ^{R 3} is a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, or has been in the 1 to 10 carbon atoms substituted by halogen It represents a linear or branched alkyl group (* represents the bonding position with L).

L is a linear or branched alkylene having 1 to 16 carbon atoms.
X represents CH _{2 -CH 2} , CH = CH or C≡C.
Y ¹ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a dialkylamino group. (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. or branched-chain acyl group, a carboxyl group, a Y ¹ -6 from a good formula Y ¹ -1 be substituted with a substituent selected from an aldehyde group and a nitro group (** represents a bonding position to X , *** represents the coupling position with ^{Y 2.).}

Y ² represents -COOH, -CR ³ = CR ^4- COOH, -CR ⁵ = CR ^6- CO-O-Y ³ or -O-CO-CR ⁵ = CR ^6- Y ³ .
R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively.
R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively.
Y ³ are each independently a halogen group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. Alternatively, a phenyl group, a biphenyl group, a naphthyl group, an alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl- which may be substituted with a substituent selected from an acyl group, a carboxyl group, an aldehyde group and a nitro group of the branched chain. Represents a cyclohexyl group or a cyclohexyl-phenyl group.

<< Manufacturing method of monomer am1 >>
[Manufacture of terminal carboxylic acid monomer having triple bond]
Specific examples of the terminal carboxylic acid type monomer (am1) having a triple bond include the following formulas (I-1) to (I-6).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group.

These monomers are produced as follows. That is, an appropriate aryl halide derivative am1-1 and an alcohol am1-2 having a triple bond at the terminal are subjected to a coupling reaction such as a sonogashira reaction in the coexistence of a metal complex, a ligand, and a base. As a result, am1-3 is manufactured. Next, the obtained ester group of am1-3 is hydrolyzed to produce am1-4. Finally, am1-4 is reacted with acrylic chloride or methacrylic chloride and acid hydrolyzed to produce (I-6) from the monomer (I-1) having a triple bond.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1). Hal is a substituent capable of desorption, for example, halogens of F, Cl, Br, I; p-toluene sulfonic acid ester group (-OSO ₂ C ₆ H _4- p-CH ₃ ), methane sulfonic acid. Sulfonic acid ester groups such as an ester group (-OSO ₂ CH ₃ ) and a trifluoromethanesulfonic acid ester group (-OSO ₂ CF _{3) are used.} Of these, Br, I, or a trifluoromethanesulfonic acid ester group is preferable from the viewpoint of reactivity. R is an alkylene group, preferably a methyl group or an ethyl group.

Specific structures of the compound am1-1 include (am1-1-1) to (am1-1-6).

(Am1-1-1) to (am1-1-3) can be purchased from a reagent company.
(Am1-1-4) can be synthesized by referring to the patent document (WO 2010071335).
(Am1-1-5) can be synthesized from the literature (Bioorganic & Medicinal Chemistry Letters, 18 (15), 4339-4343; 2008) and reacts with trifluoromethanesulfonic anhydride (am1-1-5a). It can be obtained by letting it.

(Am1-1-6) can be synthesized from the patent document (PCT Int. Appl., 2014113485) and can be obtained by reacting (am1-1-6a) with trifluoromethanesulfonic anhydride.

In the reaction between am1-1 and am1-2, a metal complex catalyst is formed and used by using an appropriate metal complex and a ligand. Usually, a palladium complex or a nickel complex is used as the metal complex, and it is preferable that a copper catalyst coexists as a co-catalyst depending on the reaction.
As the metal complex catalyst, those having various structures can be used, but it is preferable to use a so-called low valence palladium complex or nickel complex, and in particular, zero having a tertiary phosphine or a tertiary phosphite as a ligand. Valence metal complex catalysts are preferred. It is also possible to use an appropriate precursor that is easily converted into a zero-valent metal complex catalyst in the reaction system. Further, in the reaction system, a metal complex that does not contain tertiary phosphine or tertiary phosphine as a ligand is mixed with a ligand tertiary phosphine or tertiary phosphite, and tertiary phosphine or tertiary phosphine is mixed. It is also possible to generate a low valence metal complex catalyst using phosphite as a ligand.

Examples of the tertiary phosphine or tertiary phosphine that is a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-Bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphine, etc. Can be mentioned. A metal complex catalyst containing a mixture of two or more of these ligands is also preferably used.

As the metal complex catalyst, it is also preferable to use a palladium complex containing no tertiary phosphine or tertiary phosphine in combination with a metal complex containing tertiary phosphine or tertiary phosphite. In this case, the above ligands may be further combined. Examples of palladium complexes that do not contain tertiary phosphine or tertiary phosphite include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetoform) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, and chloride. Palladium, palladium-activated coal and the like can be mentioned. Examples of the palladium complex containing tertiary phosphine or tertiary phosphine as a ligand include (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and bis (triphenylphosphine) dichloropalladium. Can be mentioned.
The amount of these palladium complexes used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the compound am1-1. At the same time, the copper catalyst used as a co-catalyst is preferably monovalent, and examples thereof include copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) acetate.

Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; methylamine, dimethylamine, trimethylamine. , Ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colisine, pyrrolidine, piperidine , Morphorin, amines such as N-methylmorpholin; sodium acetate, potassium acetate, lithium acetate and the like can be used.

As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the reaction can be used. As reaction solvents, water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethylsulfoxide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), etc.), ethers ( Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) Mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.) , Solvents (acetamide, propionitrile, butyronitrile, etc.) and the like can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction and the like, and can be used alone or in combination of two or more. In some cases, the solvent can also be used as a water-free solvent by using an appropriate dehydrating agent or desiccant.

The reaction temperature can preferably be in the temperature range from −100 ° C. or higher to the boiling point temperature of the reaction solvent used, but more preferably −50 to 200 ° C., and particularly preferably 20 to 150 ° C. .. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.
The compound am1-3 obtained by the above reaction is preferably purified by distillation, recrystallization, column chromatography such as silica gel, or the like. It is preferable that recrystallization is performed at a low temperature as much as possible.

Next, the obtained ester (am1-3) is hydrolyzed by a known method to convert it into a carboxylic acid (am1-4). Subsequently, (I-1) to (I-6) can be obtained by reacting with acrylic chloride or methacrylic chloride in the presence of a base such as triethylamine, and then hydrolyzing in a mixed solution of acetonitrile and hydrochloric acid.

[Manufacture of terminal carboxylic acid type monomer having a single bond]
Specific examples of the terminal carboxylic acid type monomer (am1) having a single bond include the following formulas (II-1) to (II-6).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. )
Wherein (am1), X is _-CH 2 -CH ₂ - in the production of compounds wherein am1 from reducing the compound Am1-4, by acid hydrolysis after the reaction with acryloyl chloride or methacrylic chloride Just do it.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1).

As a method for reducing the compound am1-4, a hydrogenation reaction using palladium-activated charcoal, platinum-activated charcoal or the like, a reduction reaction carried out in the coexistence of Fe, Sn, Zn or these salts and protons, and formic acid are used as catalysts. There are reduction reactions using a hydrogen source and reactions using hydrazine as a hydrogen source. It is also possible to carry out these reactions in combination.
Among the reduction reactions exemplified above, the hydrogenation reaction is preferably used in consideration of the structure of the substrate compound am1-4 and the reactivity of the reduction reaction.
Examples of the catalyst used include commercially available activated carbon-supported metals such as palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, it does not necessarily have to be an activated carbon-supported metal catalyst such as palladium hydroxide, platinum oxide, and Raney nickel. Good results are also obtained with the use of the commonly widely used palladium-activated carbon.

As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the desired reaction can be used. For example, aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetate, N-methylpyrrolidone; ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, dioxane; pentane, hexane, heptane, petroleum ether. Aliper hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane; methyl acetate, acetate Lower fatty acid esters such as ethyl, butyl acetate and methyl propionate; nitriles such as acetonitrile, propionitrile and butyronitrile; alcohols such as methanol, ethanol and 2-propanol can be used.
These solvents can be appropriately selected in consideration of the susceptibility to reaction and the like, and can be used alone or in combination of two or more. In some cases, the solvent can also be used as a water-free solvent by using an appropriate dehydrating agent or desiccant.

In order to allow the above reduction reaction to proceed more effectively, the reaction can also be carried out in the coexistence of activated carbon. The amount of activated carbon used in this case is not particularly limited, but is 1 to 20% by weight, more preferably 1 to 10% by weight, based on the compound am1-4.
In addition, the reaction can be carried out under pressure to allow the reaction to proceed more effectively. In this case, in order to avoid reduction of benzene nuclei, the reaction is preferably carried out in a pressure range of about 20 atm (kgf), more preferably up to 10 atm.
The reaction temperature can preferably be in the temperature range from −100 ° C. or higher to the boiling point temperature of the reaction solvent used, but more preferably −50 to 150 ° C., and particularly preferably 0 to 80 ° C. .. The reaction time is 0.1 to 1000 hours, more preferably 1 to 200 hours.
The compound am1-5 obtained by the above reduction reaction is preferably purified by distillation, recrystallization, column chromatography such as silica gel, or the like.

The obtained compound am1-5 is reacted with acrylic chloride or methacrylic chloride and then hydrolyzed in a mixed solution of acetonitrile and hydrochloric acid to obtain a compound (II-1) in which _{X is −CH 2-} CH _2-. (II-6) can be produced from.

[Manufacture of cinnamic acid / cinnamic acid ester type monomer having triple bond]
Specific examples of the cinnamic acid / cinnamic acid ester type monomer (am1) having a triple bond include the following formulas (III-1) to (III-7).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group.

These monomers are produced as follows. That is, an appropriate aryl halide derivative am1-6 and an alcohol am1-2 having a triple bond at the terminal are subjected to a coupling reaction such as a sonogashira reaction in the coexistence of a metal complex, a ligand, and a base. As a result, am1-7 is manufactured.
Next, the obtained am1-7 and tert-butyl acrylate (am1-8) are subjected to a coupling reaction such as a Heck reaction in the coexistence of a metal complex, a ligand, and a base to cause am1-. 9 is manufactured.
Finally, the obtained am1-9 is reacted with acrylic chloride or methacrylic chloride and acid hydrolyzed to produce (III-5) from the monomer (III-1) having a triple bond.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1). Hal1 and Hal2 are substituents capable of elimination, for example, halogens of F, Cl, Br, I; p-toluenesulfonic acid ester group (-OSO ₂ C ₆ H _4- p-CH ₃ ), methane. Sulfonic acid ester groups such as a sulfonic acid ester group (-OSO ₂ CH ₃ ) and a trifluoromethane sulfonic acid ester group (-OSO ₂ CF ₃ ) are used. Of these, Br, I, or a trifluoromethanesulfonic acid ester group is preferable from the viewpoint of reactivity.

Specific structures of the compound am1-6 include (am1-6-1) to (am1-6-5).

(Am1-6-1) to (am1-6-3) can be purchased from reagent companies.
(Am1-6-4) can be synthesized from Patent Document (Japanese Patent Laid-Open No. 2015-078153) and can be obtained by reacting (am1-6-4a) with trifluoromethanesulfonic anhydride.

(Am1-6-5) can be synthesized from Patent Document (Japanese Patent Laid-Open No. 2015-078153) and can be obtained by reacting (am1-6-5a) with trifluoromethanesulfonic anhydride.

am1-7 can be produced by the same method as the am1-3 synthesis method using am1-6 as a raw material.

In the reaction of am1-7 with tert-butyl acrylate (am1-8), a metal complex catalyst is formed and used using an appropriate metal complex and ligand. Usually, as the metal complex, a palladium complex or a nickel complex is used.
As the metal complex catalyst, those having various structures can be used, but it is preferable to use a so-called low valence palladium complex or nickel complex, and in particular, zero having a tertiary phosphine or a tertiary phosphite as a ligand. Valence metal complex catalysts are preferred. It is also possible to use an appropriate precursor that is easily converted into a zero-valent metal complex catalyst in the reaction system. Further, in the reaction system, a metal complex that does not contain tertiary phosphine or tertiary phosphine as a ligand is mixed with a ligand tertiary phosphine or tertiary phosphite, and tertiary phosphine or tertiary phosphine is mixed. It is also possible to generate a low valence metal complex catalyst using phosphite as a ligand.

Examples of the tertiary phosphine or tertiary phosphine that is a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-Bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphine, etc. Can be mentioned. A metal complex catalyst containing a mixture of two or more of these ligands is also preferably used.

As the metal complex catalyst, it is also preferable to use a palladium complex containing no tertiary phosphine or tertiary phosphine in combination with a metal complex containing tertiary phosphine or tertiary phosphite. In this case, the above ligands may be further combined. Examples of palladium complexes that do not contain tertiary phosphine or tertiary phosphite include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetoform) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, and chloride. Palladium, palladium-activated coal and the like can be mentioned. Examples of the palladium complex containing tertiary phosphine or tertiary phosphine as a ligand include (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and bis (triphenylphosphine) dichloropalladium. Can be mentioned.
The amount of these palladium complexes used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the compound am1-1.

Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; methylamine, dimethylamine, trimethylamine. , Ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colisine, pyrrolidine, piperidine , Amines such as morpholin, N-methylmorpholin; sodium acetate, potassium acetate, lithium acetate and the like can be used.

As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the reaction can be used. As reaction solvents, water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethylsulfoxide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), etc.), ethers ( Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) Mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.) , Solvents (acetamide, propionitrile, butyronitrile, etc.) and the like can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction and the like, and can be used alone or in combination of two or more. In some cases, the solvent can also be used as a water-free solvent by using an appropriate dehydrating agent or desiccant.

The reaction temperature can preferably be in the temperature range from −100 ° C. or higher to the boiling point temperature of the reaction solvent used, but more preferably −50 to 200 ° C., and particularly preferably 20 to 150 ° C. .. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.
The compound am1-9 obtained by the above reaction is preferably purified by distillation, recrystallization, column chromatography such as silica gel, or the like. It is preferable that recrystallization is performed at a low temperature as much as possible.

Next, the obtained am1-9 is reacted with acrylic chloride or methacrylic chloride in the presence of a base such as triethylamine, and then acid hydrolyzed with formic acid to obtain (III-1) to (III-5). Can be done.

The obtained compound (III-1) having a terminal end of −CH = CHCOOH and 4-hydroxybenzoic acid tert-butyl ester are esterified with a condensing agent or the like, and then the terminal ester group is hydrolyzed with formic acid. As a result, a compound (III-6) having a terminal -CH = CH-COO-C ₆ H _{4-COOH can be produced.}

The resulting end by esterifying the compound is -CH = CHCOOH (III-1) and 4-methoxyphenol condensation agent, end is a _{-CH = CH-COO-C 6} H 4 -OMe Compound (III-7) can be produced.

[Manufacture of cinnamic acid / cinnamic acid ester type monomer having a single bond]
Specific examples of the cinnamic acid / cinnamic acid ester type monomer (am1) having a single bond include the following formulas (IV-1) to (IV-7).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group.

When the compound am1 in which X is −CH ₂ −CH ₂ − is produced, am1-11 is produced by reducing the compound am1-7.
The obtained am1-11 is Heck-reacted with am1-8 to produce am-1-12. Subsequently, (IV-5) can be produced from the compound (IV-1) which may be reacted with acrylic chloride or methacrylic chloride and then hydrolyzed with formic acid.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1).

am1-11 can be produced by the same method as the synthetic method of am1-5.
am1-12 can be produced by the same method as the synthetic method of am1-9.

(IV-1) to (IV-5) can be obtained by reacting the obtained am1-12 with acrylic chloride or methacrylic chloride in the presence of a base such as triethylamine, and then acid-hydrolyzing it with formic acid.

The obtained compound (IV-1) having a terminal end of −CH = CHCOOH and 4-hydroxybenzoic acid tert-butyl ester are esterified with a condensing agent or the like, and then the terminal ester group is hydrolyzed with formic acid. As a result, a compound (IV-6) having a terminal of −CH = CH-COO-C ₆ H _{4-COOH can be produced.}

The resulting end by esterifying the compound is -CH = CHCOOH (IV-1) and 4-methoxyphenol condensation agent, end is a _{-CH = CH-COO-C 6} H 4 -OMe Compound (IV-7) can be produced.

[Production of non-carboxylic acid type monomer having triple bond]
Specific examples of the non-carboxylic acid type monomer (am1) having a triple bond include the following formulas (V-1) to (V-6).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group.

These monomers are produced as follows. That is, a coupling reaction such as a sonogashira reaction between an appropriate aryl halide am1-15 and an alcohol protecting group am1-14 having a triple bond at the terminal in the coexistence of a metal complex, a ligand, and a base. By performing the above, am1-16 is manufactured. In addition, am1-16 can also be produced by combining the Sonogashira reaction and the Suzuki-Miyaura reaction.
Next, am1-18 is produced by reacting the obtained am1-16 with a cinnamic acid derivative (am1-17) in the presence of a condensing agent and a base.

Finally, the protecting group of am1-18 can be deprotected and reacted with acrylic chloride or methacrylic chloride in the presence of basic substances to produce (V-6) from the monomer (V-1) having a triple bond. can.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1). Ar ₁ represents a divalent organic group having an aromatic ring. Hal, Hal ₁ and Hal ₂ are substituents capable of elimination, for example, halogens of F, Cl, Br, I; p-toluene sulfonic acid ester groups (-OSO ₂ C ₆ H _4- p-CH). ₃ ), sulfonic acid ester groups such as methanesulfonic acid ester group (-OSO ₂ CH ₃ ) and trifluoromethanesulfonic acid ester group (-OSO ₂ CF ₃ ) are used. Of these, Br, I, or a trifluoromethanesulfonic acid ester group is preferable from the viewpoint of reactivity. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl. PG represents a protecting group.

am1-14 is obtained by protecting the terminal alcohol of am1-2 with a suitable protecting group (PG). Examples of types of protecting groups (PG) are listed in GREENE'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE co-authored, A John Wiley & Sons, Inc., Publication). Protecting groups are preferred. In particular, protection with 3,4-dihydro-2H-pyran is preferred.

Specific examples of am1-15 include (am1-15-1) to (am1-15-4), (am1-6-4a), and (am1-6-5a).

(Am1-15-1) to (am1-15-4) can be purchased from reagent companies.
am1-16 can be produced from am1-15 as a raw material by the same method as the am1-3 synthesis method.
For am1-16, am1-6 and am1-14 are reacted with Suzuki-Miyaura using an organometallic reagent (am1-16b) and a metal catalyst after obtaining am1-16a by the same method as the am1-3 synthesis method. Can be obtained by

In the formula, Ar ₁ represents a divalent organic group having an aromatic ring. Hal is a substituent capable of desorption, for example, halogens of F, Cl, Br, I; p-toluene sulfonic acid ester group (-OSO ₂ C ₆ H _4- p-CH ₃ ), methane sulfonic acid. Sulfonic acid ester groups such as an ester group (-OSO ₂ CH ₃ ) and a trifluoromethanesulfonic acid ester group (-OSO ₂ CF _{3) are used.} Of these, Br, I, or a trifluoromethanesulfonic acid ester group is preferable from the viewpoint of reactivity. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl. PG represents a protecting group.

The coupling reaction (Suzuki-Miyaura reaction) uses an appropriate metal complex and ligand as a catalyst. In some cases, the reaction proceeds without a ligand. Usually, a palladium complex or a nickel complex is used. As the catalyst, those having various structures can be used, but it is preferable to use a so-called low valence palladium complex or nickel complex, and in particular, a zero-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand. Is preferable. It is also possible to use a suitable precursor that is easily converted to a zero-valent complex in the reaction system. Further, in the reaction system, a complex that does not contain tertiary phosphine or tertiary phosphine as a ligand is mixed with tertiary phosphine or tertiary phosphite, and tertiary phosphine or tertiary phosphite is used as a ligand. It is also possible to generate a low valence complex. Examples of the tertiary phosphine or tertiary phosphite that is a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphine, triethylphosphine, triphenylphosphine, etc. A complex containing a mixture of two or more of these ligands is also preferably used. It is also a preferable embodiment that a palladium complex containing no tertiary phosphine or tertiary phosphine, a complex containing tertiary phosphine or tertiary phosphine, and the above-mentioned ligand are used in combination as a catalyst. Examples of the complex that does not contain tertiary phosphine or tertiary phosphite used in combination with the above-mentioned ligands include bis (benzilidenacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetoformer) dichloropalladium, and bis (benzo). Nitrile) Dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetethane complex, palladium-activated coal, nickel chloride, nickel iodide, etc., and as a complex already containing tertiary phosphine or tertiary phosphite as a ligand. Dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1 , 3-Bis (diphenylphosphino) propane] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride and the like, but are not limited thereto. The amount of these palladium complex and nickel complex used may be a so-called catalytic amount, and in general, 20 mol% or less with respect to the substrate is sufficient, and usually 10 mol% or less.

Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, methylamine, and dimethyl. Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colisine, etc. In addition to the amines of, sodium acetate, potassium acetate, lithium acetate and the like can also be used.

The solvent is one that is stable under the reaction conditions, is inert and does not interfere with the reaction. Water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic Hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, etc.) , Carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetriform, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 20 to 120 ° C.
The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.
The am1-16 obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction.

Appropriate condensing agents and bases are used in the reaction of am1-16 with 4-methoxycinnamic acid (am1-17). Examples of the condensing agent include N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and N- [3- (dimethylamino) propyl. ] -N'-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide methiozide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-(2-) Morphorinoethyl) carbodiimides include meth-p-toluenesulfonate, N, N'-di-tert-butyl carbodiimides, N, N'-di-p-tolyl carbodiimides and other carbodiimides. In addition to carbodiimide, triazine-based condensing agents, acid chlorides, acid anhydrides and other condensing agents can be mentioned. As the base, for example, a primary amine, a secondary amine, a tertiary amine or an aromatic amine and the amine salt thereof can be used, and from the viewpoint of yield, the tertiary amine or aromatic amine and the amine are used. Salt is more preferred. Specifically, trimethylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, triethylamine, N, N-dimethylpropylamine, N, N-dimethylbutylamine, N, N-dimethylpentylamine, N, N -Diethylpropylamine, N, N-dipropylethylamine, N, N-dipropylmethylamine, N, N-diethylpentylamine, N-ethyl-N-methylpentylamine, tributylamine, N, N-dibutylmethylamine , N, N-dibutylethylamine, N, N-dibutylpropylamine, N-ethyl-N-methylpropylamine, N, N-dipropylmethylamine, N, N-dipropylethylamine, tripropylamine, triisopropylamine , N-Methyldiisopropylamine, N-ethyldiisopropylamine, N-propyldiisopropylamine, N-butyldiisopropylamine, pyridine, N-methylpyridine, 2-chloropyridine, 2-bromopyridine, piperidine, pyrimidine, quinoline, acrydin, Examples thereof include N, N-dimethyl-4-aminopyridine, picolin, bipyridine, 2,6-rutidine, pyridinium chlorochromate, pyridinium paratoluenesulfonate and other tertiary amines or aromatic amines, and their amine salts. In particular, N, N-dimethyl-4-aminopyridine is preferable.

As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the reaction can be used. For example, aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetate, N-methylpyrrolidone; ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, dioxane; pentane, hexane, heptane, petroleum ether. Fatal hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane; methyl acetate, acetate Lower fatty acid esters such as ethyl, butyl acetate and methyl propionate; acetonitrile, propionitrile, butyronitrile and the like can be used.
These solvents can be appropriately selected in consideration of the susceptibility to reaction and the like, and can be used alone or in combination of two or more. In some cases, the solvent can also be used as a water-free solvent by using an appropriate dehydrating agent or desiccant.

The reaction temperature can preferably be in the temperature range from −100 ° C. or higher to the boiling point temperature of the reaction solvent used, but more preferably −50 to 200 ° C., and particularly preferably 20 to 150 ° C. .. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.
The compound am1-18 obtained by the above reaction is preferably purified by distillation, recrystallization, column chromatography such as silica gel, or the like.

The deprotection conditions for the protecting groups of am1-18 are listed in GREENE'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE, A John Wiley & Sons, Inc., Publication). The reaction conditions are preferable. In particular, a method of deprotecting with a catalytic amount of pyridinium p-toluenesulfonate in ethanol is preferable.

(V-6) can be obtained from (V-1) by reacting with acrylic chloride or methacrylic chloride in the presence of a base such as triethylamine.

[Production of non-carboxylic acid type monomer having a single bond]
Specific examples of the non-carboxylic acid type monomer (am1) having a single bond include the following formulas (VI-1) to (VI-6).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group.

When producing the compound am1 in which X is −CH ₂ −CH ₂ −, after producing am1-20 by reducing the compound am1-16, a condensation reaction with a cinnamic acid derivative using a condensing agent is performed. (VI-6) can be produced from (VI-1) by reacting with a deprotection reaction, acrylic chloride or methacryl chloride.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents a hydrogen or methyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1).

am1-20 can be produced by the same production method as the am1-5 synthesis method.
am1-21 can be produced by the same production method as the am1-18 synthesis method.
am1-22 can be produced by the same production method as the am1-19 synthesis method.
(VI-6) can be obtained from (VI-1) by reacting am1-22 with acrylic chloride or methacrylic chloride in the presence of a base such as triethylamine.

[Manufacture of α-methylene-γ-butyrolactone type monomer]
Specific examples of the α-methylene-γ-butyrolactone type monomer (am1) include the following formulas (VII-1) to (VII-6). In the formula, Q1 is a linear alkylene having 1 to 16 carbon atoms. Wherein, Q ² is a linear alkylene group having 1 to 4 carbon atoms. R represents a methyl group or an ethyl group. Examples of R include a hydrogen atom or a C1-4 alkyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1).

The α-methylene-γ-butyrolactone compound (PL-2) can be synthesized by combining techniques in synthetic organic chemistry, and the synthesis method is not particularly limited. After introducing an alkyl halide (am1-23) into am1-1, am1-6, and am1-15 by a sonogashira reaction instead of am1-2 and am1-14, a known synthesis as shown in the following formula. After conversion to acetal and ketal derivatives using the method, the metal reagents and acrylic acid derivatives (am1-24) are reacted under acidic conditions to cause (VII-1), (VII-2), (VII-5). , (VII-6) can be synthesized (references: eg, P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990)). Further, (VII-3) and (VII-4) can be synthesized by inducing them into an α-methylene-γ-butyrolactone compound and then acid-hydrolyzing them with formic acid.

Wherein, Q ² is a linear alkylene group having 1 to 4 carbon atoms. R represents a methyl group or an ethyl group. Examples of R include a hydrogen atom or a C1-4 alkyl group. Ar represents ^{(Y 1 -1) ~ (Y} 1 -6) of formula (am1). Hal, Hal ₁ , and Hal ₂ are substituents capable of elimination, for example, halogens of F, Cl, Br, I; p-toluene sulfonic acid ester group (-OSO ₂ C ₆ H _4- p-CH _3). ), Sulfonic acid ester group such as methanesulfonic acid ester group (-OSO ₂ CH ₃ ), trifluoromethanesulfonic acid ester group (-OSO ₂ CF ₃ ) and the like are used. Of these, Br, I, or a trifluoromethanesulfonic acid ester group is preferable from the viewpoint of reactivity. Y is Cl or Br.

Examples of the acrylic acid derivative (am1-24) represented by the above α-methylene-γ-butyrolactone compound synthesis include 2- (chloromethyl) acrylic acid, 2- (chloromethyl) methyl acrylate, and 2- (chloromethyl). Ethyl acrylate, 2- (bromomethyl) acrylic acid, methyl 2- (bromomethyl) acrylate, ethyl 2- (bromomethyl) acrylate and the like can be used.

As the metal reagent, tin-based compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, tin chloride pentahydrate, indium powder, zinc powder and the like can be used.

As the acid, an inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, phosphoric acid and ammonium chloride, an acidic resin such as Amberlyst 15, and an organic acid such as p-toluenesulfonic acid, acetic acid and formic acid can be used.

The solvent is one that is stable under the reaction conditions, is inert and does not interfere with the reaction. Water, alcohols, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (Pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, tetrachloride, etc.) Carbon, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetriform, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more. Tetrahydrofuran and water are preferred.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably 20 to 100 ° C.
The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 60 hours.

The α-methylene-γ-butyrolactone compound obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction to obtain high purity.

The solvent used for cleaning is not particularly limited, but is, for example, hydrocarbons such as hexane, heptane or toluene, halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4. -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof. Examples thereof are preferably alcohols such as methanol or ethanol and 2-propanol.

The solvent used for recrystallization is not particularly limited as long as the α-methylene-γ-butyrolactone compound dissolves during heating and precipitates during cooling, but is not particularly limited, and for example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1,2-. Halogen-based hydrocarbons such as dichloroethane or chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile , Methanol or ethanol, alcohols such as 2-propanol and mixtures thereof, preferably alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol, 2-propanol, hexane or mixtures thereof. ..

[Liquid crystal side chain monomer]
The liquid crystal side chain monomer is 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.
As a mesogen group having a side chain, even if it is a group having a mesogen structure by itself such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid. good. The following structure is preferable as the mesogen group having a side chain.

More specific examples of liquid side chain monomers include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radically polymerizable groups. It is preferable that the structure has a polymerizable group composed of at least one selected from the group consisting of siloxane and a side chain composed of at least one of the above formulas (21) to (31).

The side chain type polymer (A) can be obtained by the polymerization reaction of the photoreactive side chain monomer exhibiting the liquid crystal property described above. Further, it can be obtained by copolymerizing a photoreactive side chain monomer that does not exhibit liquidity and a liquid crystal side chain monomer, or by copolymerizing a photoreactive side chain monomer that exhibits liquidity and a liquid crystal side chain monomer. can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available radical polymerization-reactive monomers.
Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples thereof include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-butyl. Methacrylate, Cyclohexyl methacrylate, Isobornyl methacrylate, 2-Methylethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-Methyl-2-adamantyl methacrylate, 2- Examples thereof include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like. (Meta) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The content of the side chain represented by the above formula (a) in the side chain polymer of the present invention is preferably 5 mol% 100 mol%, more preferably 10 mol% to 90 mol%, and 15 mol% to 85. More preferably mol%.
The content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 mol% to 90 mol%, more preferably 15 mol% to 85 mol%, and 20 mol% from the viewpoint of liquid crystal orientation. -80 mol% is more preferred.
The content of the liquid crystal side chain in the side chain polymer of the present invention is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 90 mol%, and 15 mol% to 15 mol% from the viewpoint of liquid crystal orientation. 85 mol% is more preferred.
The side chain type polymer of the present invention may contain other side chains other than the side chain represented by the above formula (a), the photoreactive side chain and the liquid crystal side chain. The content is the remaining portion when the total content of the side chain, the photoreactive side chain and the liquid crystal side chain represented by the above formula (a) is less than 100 mol%.

The method for producing the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
As the polymerization initiator for radical polymerization, known compounds such as a radical polymerization initiator and a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumenehydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.) and azo radical compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used alone or in combination of two or more.

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 and 2-hydroxy. -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri ( t-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 (trichloromethyl) -s-triazine, 2 -(2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-Mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bi Su (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2' -Bimidazole, 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-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2,4-cyclopentadiene-1- Il) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (3,4'-di ( Methylcarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3- (3-) Methyl-3H-benzothiazole-2-ylidene) -1-naphthalen-2-yl-etanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -iriden) -1- (2-) Benzoyl) Etanone and the like can be mentioned. These compounds may be used alone or in admixture of two or more.

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

The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the produced polymer dissolves. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide , Γ-Butylollactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, methyl cellosolve acetate, ethyl cellosolve acetate, 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether , Diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
Further, in radical polymerization, oxygen in an organic solvent causes an inhibition of the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.

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

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.

[Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side-chain polymer capable of expressing liquidity obtained by the above reaction, the reaction solution is put into a poor solvent and their weights are increased. The coalescence may be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the purification efficiency is further improved.

The molecular weight of the side chain polymer (A) of the present invention is measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, the workability at the time of forming the coating film, and the uniformity of the coating film. The weight average molecular weight obtained is preferably 2000 to 2000000, more preferably 5000 to 150,000. Alternatively, the weight average molecular weight is preferably 2000 to 1000000, more preferably 5000 to 20000.
In the side chain type polymer which is the component (A) of the present invention, the content of the side chain represented by the formula (a) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and 20 to 20 mol%. 80 mol% is more preferred.

<< (B) Organic Solvent >>
The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglime, 4-hydroxy-4-methyl-2-pentanone, propylene glycol mono Acetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Examples thereof include dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, and tripropylene glycol methyl ether. These may be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above components (A), (B) and (C). Examples thereof include solvents and compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and the like. , Not limited to this.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.
For example, 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 mono. Isopropyl 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tri Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amylacetate, butylbutyrate, butyl ether, diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy- 2-propanol, 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- Low levels of 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate ester, ethyl lactate ester, n-propyl ester lactate, n-butyl ester lactate, isoamyl lactate ester, etc. Examples thereof include a solvent having a surface tension.

These poor solvents may be used alone or in admixture of a plurality of types. When the above-mentioned solvent is used, it is preferably 5% by mass to 80% by mass, more preferably 5% by mass, so as not to significantly reduce the solubility of the whole solvent contained in the polymer composition. Is 20% by mass to 60% by mass.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafuck (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431. (Sumitomo 3M), Asahi Guard (registered trademark) AG710 (Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by AGC Seimi Chemical), etc. Be done. The ratio of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, and more preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. It is a mass part.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. , N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl- 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-aminopropyltrimethoxy Examples thereof include silane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, the following phenoplast-based or epoxy group-containing compounds are added for the purpose of preventing deterioration of electrical characteristics due to the backlight when the liquid crystal display element is configured. The agent may be contained in the polymer composition. Specific phenoplast-based 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N', N',-tetraglycidyl-4,4'-diaminodiphenylmethane Etc. are exemplified.

When a compound that improves adhesion to a substrate is used, the amount used is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. , More preferably 1 part by mass to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal display may deteriorate.

A photosensitizer can also be used as the additive. Colorless sensitizers and triplet sensitizers are preferred.
Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscmarin, aromatic 2-hydroxyketone, and amino substitutions. , Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthron, thiazolin (2-benzoylmethylene-3) -Methyl-β-naphthiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazolin, 2- (α-naphthoylmethylene) -3-methylbenzothiazolin, 2- (4-biphenoylmethylene)- 3-Methylbenzothiazolin, 2- (β-naphthoyl methylene) -3-methyl-β-naphthiazoline, 2- (4-biphenoyl methylene) -3-methyl-β-naphthiazoline, 2- (p-fluoro) Benzoylmethylene) -3-methyl-β-naphthiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α) -Naftylmethylene) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2-( 4-Bifenoylmethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaften (5-nitroacenaften), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoinalkyl ether, N-alkylated phthalone, Acetphenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyrane, azoindidine, methylcoumarin, etc. There is.
Preferred are aromatic 2-hydroxyketones (benzophenone), coumarin, ketocoumarin, carbonyl biscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In addition to the above-mentioned polymer compositions, dielectrics and conductive substances can be used for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and density of the film when it is formed into a liquid crystal alignment film.

[Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention includes the above-mentioned component (A), the above-mentioned solvent or compound that improves the film thickness uniformity and surface smoothness, and the compound that improves the adhesion between the liquid crystal alignment film and the substrate. Etc. are preferably prepared as a solution dissolved in an organic solvent. Here, the content of the component (A) is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, in addition to the component (A), other polymers may be mixed as long as the liquid crystal display ability and the photosensitive performance are not impaired. At that time, the content of the other polymer 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 polymers that are composed of poly (meth) acrylate, polyamic acid, polyimide, etc., and are not photosensitive side chain polymers capable of exhibiting liquid crystallinity.

<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for manufacturing a substrate having a liquid crystal alignment film of the present invention is
[I] A polymer composition characterized by containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent for driving a transverse electric field. A process of forming a coating film by applying it on a substrate having a conductive film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
Have.
Through the above steps, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which orientation control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In the second aspect of the present invention, the method for producing a substrate having a liquid crystal alignment film of the present invention is:
[I] A polymer composition characterized by containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent for driving a transverse electric field. A process of forming a coating film by applying it on a substrate having a conductive film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
Have.
Through the above steps, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which orientation control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a transverse electric field drive type liquid crystal display element can be obtained.
As the second substrate, the above steps [I] to [III] (for driving a transverse electric field) are used, except that a substrate having no conductive film for driving a transverse electric field is used instead of the substrate having a conductive film for driving a transverse electric field. Since a substrate having no conductive film is used, for convenience, in the present application, steps [I'] to [III'] may be abbreviated) to have a liquid crystal alignment film to which orientation control ability is imparted. 2 substrates can be obtained.

The method for manufacturing a transverse electric field drive type liquid crystal display element is as follows.
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so as to face each other so that the liquid crystal alignment films of the first and second substrates face each other via a liquid crystal display;
Have. As a result, a horizontal electric field drive type liquid crystal display element can be obtained.

Hereinafter, each of the steps [I] to [III] and [IV] included in the production method of the present invention will be described.
<Step [I]>
In step [I], a polymer composition containing a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and an organic solvent is applied onto a substrate having a conductive film for driving a transverse electric field. To form a coating film.

<Board>
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 that case, the present invention is not particularly limited, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
Further, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductor for driving a transverse electric field>
The substrate has a conductive film for driving a transverse electric field.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: indium tin oxide) and IZO (Indium Zinc Oxide: indium zinc oxide) when the liquid crystal display element is a transmissive type.
Further, in the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but the conductive film is not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

The method of applying the above-mentioned polymer composition on a substrate having a conductive film for driving a transverse electric field is not particularly limited.
Industrially, the coating method is generally performed by screen printing, offset printing, flexographic printing, inkjet method, or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotary coating method), a spray method, and the like, and these may be used depending on the purpose.

After applying the polymer composition on a substrate having a conductive film for driving a transverse electric field, the temperature is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. A coating can be obtained by evaporating the solvent at 150 ° C. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, the thickness is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. Is.
It is also possible to provide a step of cooling the substrate on which the coating film is formed to room temperature after the step [I] and before the subsequent step [II].

<Step [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays from a certain direction via a polarizing plate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film used. Then, for example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is the polarized ultraviolet rays that realize the maximum value of ΔA (hereinafter, also referred to as ΔAmax), which is the difference between the ultraviolet absorptivity in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorptivity in the vertical direction in the coating film. The amount is preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.

<Step [III]>
In step [III], the coating film irradiated with ultraviolet rays polarized in step [II] is heated. Orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is exhibited.

The heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as the liquid crystal display temperature). In the case of a thin film surface such as a coating film, the liquid crystal display temperature on the coating film surface may be lower than the liquid crystal display temperature when a photosensitive side chain polymer capable of exhibiting liquid crystal properties is observed in bulk. is expected. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal appearance temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal development temperature of the side chain polymer to be used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. The temperature is preferably in the range up to the temperature. If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high above the above temperature range, the state of the coating film is in a state. Tends to be close to an isotropic liquid state (isotropic phase), in which case self-assembly can make it difficult to reorient in one direction.
The liquid crystal development temperature is equal to or higher than the glass transition temperature (Tg) at which the side chain polymer or the coating surface undergoes a phase transition from the solid phase to the liquid crystal phase, and the liquid crystal phase to the isotropic phase (isotropic phase). A temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. Then, a substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<Step [IV]>
In the [IV] step, the same as the substrate (first substrate) having the liquid crystal alignment film on the conductive film for driving the transverse electric field obtained in [III], and the above [I'] to [III']. The obtained substrate with a liquid crystal alignment film (second substrate) having no conductive film is placed facing each other so that both liquid crystal alignment films face each other via the liquid crystal, and the liquid crystal cell is formed by a known method. This is a step of manufacturing and manufacturing a transverse electric field driven liquid crystal display element. In steps [I'] to [III'], except that in step [I], a substrate having no transverse electric field driving conductive film was used instead of the substrate having the transverse electric field driving conductive film. It can be carried out in the same manner as in steps [I] to [III]. Since the only difference between the steps [I] to [III] and the steps [I'] to [III'] is the presence or absence of the conductive film described above, the description of the steps [I'] to [III'] is omitted. do.

To give an example of manufacturing a liquid crystal cell or a liquid crystal display element, the above-mentioned first and second substrates are prepared, spacers are sprayed on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is on the inside. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure to seal it, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacer is sprayed and then the substrate is bonded and sealed. , Etc. can be exemplified. At this time, it is preferable to use a substrate having an electrode having a structure like a comb tooth for driving a transverse electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a substrate with a coating film of the present invention, the polymer composition is applied onto the substrate to form a coating film, and then polarized ultraviolet rays are irradiated. Next, by heating, highly efficient anisotropy is introduced into the side chain type polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal orientation control ability is manufactured.
The coating film used in the present invention realizes highly efficient introduction of anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the photoreaction of side chains and self-assembly based on liquid crystallinity. .. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are emitted. After irradiating and then heating, a liquid crystal display element is produced.

Therefore, the coating film used in the method of the present invention is a liquid crystal alignment film having excellent orientation control ability because anisotropy is introduced with high efficiency by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment. can do.

Then, in the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film and the heating temperature in the heat treatment are optimized. As a result, highly efficient introduction of anisotropy into the coating film can be realized.

The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes a photocrossing reaction, a photoisomerization reaction, or a photofleece rearrangement reaction in the coating film. Corresponds to the irradiation amount of polarized ultraviolet rays that optimizes the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, if the number of photosensitive groups in the side chain that undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photoFries rearrangement reaction is small, the amount of photoreaction is not sufficient. .. In that case, even if it is heated after that, sufficient self-organization does not proceed. On the other hand, in the coating film used in the present invention, as a result of irradiating a structure having a photocrosslinkable group with polarized ultraviolet rays, if the photosensitive group of the side chain undergoing the crosslink reaction becomes excessive, the crosslink reaction between the side chains occurs. It will go too far. In that case, the resulting membrane may become rigid and hinder the progress of self-assembly by subsequent heating. Further, in the coating film used in the present invention, as a result of irradiating a structure having a photo Fries rearrangement group with polarized ultraviolet rays, if the photosensitive groups of the side chains that undergo a photo Fries rearrangement reaction become excessive, the liquid crystal property of the coating film becomes high. Will drop too much. In that case, the liquid crystal property of the obtained film is also lowered, which may hinder the progress of self-assembly due to the subsequent heating. Furthermore, when irradiating a structure having a photo Fries rearrangement group with polarized ultraviolet rays, if the amount of ultraviolet rays irradiated is too large, the side chain polymer is photodecomposed, which hinders the progress of self-assembly due to subsequent heating. May become.

Therefore, in the coating film used in the present invention, the optimum amount of the photosensitive group of the side chain undergoing a photocrosslinking reaction, a photoisomerization reaction, or a photofreeze rearrangement reaction by irradiation with polarized ultraviolet rays is the side chain type polymer film. It is preferably 0.1 mol% to 40 mol%, and more preferably 0.1 mol% to 20 mol% of the photosensitive groups of the above. By setting the amount of photosensitive groups in the side chain that photoreacts within such a range, self-assembly in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy can be formed in the film. Become.

In the coating film used in the method of the present invention, a photocrosslinking reaction, a photoisomerization reaction, or a photofleece rearrangement reaction of a photosensitive group in the side chain of a side chain type polymer film is performed by optimizing the irradiation amount of polarized ultraviolet rays. Optimize the amount of. Then, together with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, the suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, after irradiation with polarized ultraviolet rays, the absorption of ultraviolet rays in the direction parallel to the polarization direction of the polarized ultraviolet rays and the absorption of ultraviolet rays in the direction perpendicular to the polarization direction are measured, respectively. From the measurement result of ultraviolet absorption, 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, is evaluated. 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 are obtained. In the production method of the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined based on the amount of polarized ultraviolet rays that realizes this ΔAmax.

In the production method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realize ΔAmax, and is preferably 1% to 70%. It is more preferably within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays in the range of 1% to 50% of the amount of polarized ultraviolet rays that realize ΔAmax is 0. It corresponds to the amount of polarized ultraviolet rays that photocrosslink 1 mol% to 20 mol%.

Based on the above, in the production method of the present invention, in order to realize highly efficient introduction of anisotropy into the coating film, the suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is better to determine. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., it is desirable that the heating temperature after irradiation with polarized ultraviolet rays is 90 ° C. to 190 ° C. By doing so, the coating film used in the present invention is imparted with greater anisotropy.

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

As described above, the substrate for the transverse electric field driven liquid crystal display element manufactured by the method of the present invention or the transverse electric field driven liquid crystal display element having the substrate has excellent reliability and has a large screen and high definition. It can be suitably used for LCD TVs and the like.
Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The structure of the (meth) acrylate compound used in the examples is shown below.
<Polymerizable compound>

MA-1 was synthesized by the synthetic method described in Patent Document (WO2011-084546).
MA-2 was synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 9-118717).
MA-3 was synthesized by the same synthesis method as MA-2.
MA-4 to MA-8 are novel compounds that have not been published in the literature, and the synthetic method will be described in detail below.
MA-9 was synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 2006-308878).

The products described in Synthesis Examples 1 to 5 below were ^{identified by 1 1} H-NMR analysis (analytical conditions are as follows).
Equipment: Varian NMR System 400 NB (400 MHz)
Measuring solvent: CDCl _3, DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)
<Synthesis Example 1 Synthesis of MA-4>

<Synthesis of MA-4A>
Ethyl 4-bromobenzoate (78.7 g, 344 mmol) and diethylamine (125.8 g), 5-hexin-1-ol (43.8 g), copper iodide (2.6 g) in tetrahydrofuran (393.5 g). Was prepared to create a nitrogen atmosphere, and then bis (triphenylphosphine) palladium (II) dichloride (4.8 g) was added and reacted at 60 ° C. for 7 hours. After completion of the reaction, 3.9 g of activated carbon (brand: special dried Shirasagi product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Subsequently, tetrahydrofuran was removed by concentration under reduced pressure, diluted with ethyl acetate, and then washed with pure water three times. 3.9 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the obtained organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain 103 g of MA-4A (coarse). Yield: 122%, Properties: Brown oily compound).

<Synthesis of MA-4B>
Dissolve MA-4A (50.4 g) obtained above in methanol (151.2 g) and pure water (100.8 g), add potassium hydroxide (17.2 g), and add potassium hydroxide (17.2 g) for 2 hours under room temperature conditions. It was reacted. After completion of the reaction, ethyl acetate and a 3.0 M aqueous hydrochloric acid solution were added to acidify the aqueous phase side, and then the aqueous hydrochloric acid phase was removed. Subsequently, after washing the organic phase twice with pure water, 2.5 g of activated carbon (brand: specially made Shirasagi dried product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Then, it was concentrated under reduced pressure to obtain light brown crystals. After adding isopropyl alcohol to the obtained crystals to make a uniform solution at 60 ° C., recrystallization was performed by adding acetonitrile as a poor solvent, and the mixture was filtered and dried to obtain 25.5 g of MA-4B (25.5 g). 2-step yield: 70%, properties: light gray crystals).

<Synthesis of MA-4>
MA-4B (24.4 g, 112 mmol) and triethylamine (28.5 g) obtained above were charged in tetrahydrofuran (146.4 g), and methacryloyl chloride (25.9 g) was added dropwise under nitrogen-atmospheric ice-cooled conditions. bottom. After completion of the dropping, the reaction was carried out under room temperature conditions for 17 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate, washed 3 times with pure water, and the organic phase was concentrated under reduced pressure to obtain a yellow oily compound. Subsequently, the oily compound was diluted with acetonitrile (78.3 g) and a 1.0 M aqueous hydrochloric acid solution (48.8 g), and reacted at 50 ° C. for 2 days. After completion of the reaction, the reaction solution was diluted with ethyl acetate, the aqueous hydrochloric acid phase was removed, and then the mixture was washed 3 times with pure water. 1.3 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the recovered organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain a brown oily compound. Subsequently, acetonitrile was added and heated to 50 ° C. to obtain a uniform solution, ice-cooled to precipitate crystals, and filtration to obtain a crude product. Subsequently, the obtained crude product was subjected to slurry washing with a mixed solution of acetonitrile and tetrahydrofuran, filtered and dried to obtain 12.4 g of MA-4 (yield: 39%, properties: white crystals).
^{1 1} H-NMR (400 MHz) in DMSO-d ₆ : 1.61-1.63 ppm (m, 2H), 1.64-1.78 ppm (m, 2H), 1.89 ppm (s, 3H), 2 .51-2.54ppm (m, 2H), 4.16ppm (t, 2H), 5.67-5.69ppm (m, 1H), 6.04-6.05ppm (m, 1H), 7.48 -7.51 ppm (m, 2H), 7.88-7.91 ppm (m, 2H), 13.1 ppm (s, 1H).
<Synthesis Example 2 Synthesis of MA-5>

<Synthesis of MA-5A>
Ethyl 4-bromobenzoate (68.7 g, 300 mmol) and diethylamine (109.7 g), 6-heptin-1-ol (43.7 g), copper iodide (2.3 g) in tetrahydrofuran (343.5 g). Was prepared to create a nitrogen atmosphere, and then bis (triphenylphosphine) palladium (II) dichloride (4.2 g) was added and reacted at 60 ° C. for 23 hours. After completion of the reaction, 6.8 g of activated carbon (brand: special dried Shirasagi product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Subsequently, tetrahydrofuran was removed by concentration under reduced pressure, diluted with ethyl acetate, and then washed with pure water three times. 6.8 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the obtained organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain 98.3 g of MA-5A. (Crude yield: 126%, Properties: brown oily compound).

<Synthesis of MA-5B>
Dissolve MA-5A (49.3 g) obtained above in methanol (98.6 g) and pure water (98.6 g), add potassium hydroxide (15.0 g), and add potassium hydroxide (15.0 g) for 2 hours under room temperature conditions. It was reacted. After completion of the reaction, ethyl acetate and a 3.0 M aqueous hydrochloric acid solution were added to acidify the aqueous phase side, and then the aqueous hydrochloric acid phase was removed. Subsequently, after washing the organic phase twice with pure water, 4.9 g of activated carbon (brand: specially made Shirasagi dried product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Then, it was concentrated under reduced pressure to obtain light brown crystals. After adding isopropyl alcohol to the obtained crystals to make a uniform solution at 60 ° C., acetonitrile was added as a poor solvent for recrystallization, and the crystals were filtered and dried to obtain 25.1 g of MA-5B (25.1 g). 2-step yield: 72%, properties: pale yellow crystals).

<Synthesis of MA-5>
Tetrahydrofuran (125.2 g), MA-5B (25.1 g, 108 mmol) obtained above and triethylamine (30.4 g) were charged, and methacryloyl chloride (24.9 g) was added dropwise under nitrogen-atmospheric ice-cooled conditions. .. After completion of the dropping, the reaction was carried out under room temperature conditions for 4 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate, washed 3 times with pure water, and the organic phase was concentrated under reduced pressure to obtain a yellow oily compound. Subsequently, the oily compound was diluted with acetonitrile (76.0 g) and a 1.0 M aqueous hydrochloric acid solution (50.0 g), and reacted at 50 ° C. for 2 days. After completion of the reaction, the reaction solution was diluted with ethyl acetate, the aqueous hydrochloric acid phase was removed, and then the mixture was washed 3 times with pure water. 1.3 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the recovered organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain a brown oily compound. Subsequently, acetonitrile was added and heated to 50 ° C. to obtain a uniform solution, ice-cooled to precipitate crystals, and filtration to obtain a crude product. The obtained crude product was recrystallized from a mixed solution of acetonitrile and tetrahydrofuran, filtered and dried to obtain 12.6 g of MA-5 (yield: 39%, properties: white crystals).
^{1 1} H-NMR (400 MHz) in DMSO-d ₆ : 1.44-1.71 ppm (m, 6H), 1.87 ppm (s, 3H), 2.46-2.52 ppm (m, 2H), 4 .12ppm (t, 2H), 5.65-5.66ppm (m, 1H), 6.01-6.02ppm (m, 1H), 7.46-7.50ppm (m, 2H), 7.89 -7.91 ppm (m, 2H), 13.1 ppm (s, 1H)
<Synthesis Example 3 Synthesis of MA-6>

<Synthesis of MA-4B>
MA-4A (47.1 g) was dissolved in methanol (94.2 g) and pure water (93.1 g), potassium hydroxide (17.6 g) was added, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, ethyl acetate and a 3.0 M aqueous hydrochloric acid solution were added to acidify the aqueous phase side, and then the aqueous hydrochloric acid phase was removed. Subsequently, after washing the organic phase with pure water three times, 4.7 g of activated carbon (brand: specially made Shirasagi dried product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Then, it was concentrated under reduced pressure to obtain a crude product. Subsequently, the obtained crude product was dissolved in ethyl acetate by heating at 60 ° C., ice-cooled to precipitate crystals, filtered and dried to obtain 24.9 g of MA-4B.

<Synthesis of MA-6A>
Tetrahydrofuran (124.5 g), MA-4B (24.9 g) obtained above and 5% palladium carbon powder (hydrous product) STD type (brand: N.E. Chemcat, Inc., 2.5 g) were charged, and 0. The reaction was carried out under 5 MPa hydrogen pressure conditions for 17 hours. After completion of the reaction, filtration and slurry washing with acetonitrile were carried out to obtain 20.7 g of MA-6A (three-step yield: 53%, properties: pale yellow crystals).

<Synthesis of MA-6>
MA-6A (20.7 g), triethylamine (23.6 g) and N, N-dimethyl-4-aminopyridine (0.53 g) were charged in tetrahydrofuran (124.2 g) under ice-cooled conditions in a nitrogen atmosphere. Methacryloyl chloride (22.4 g) was added dropwise, and the mixture was reacted under room temperature conditions for 2 hours. After completion of the reaction, the mixture was diluted with ethyl acetate, washed once with a 1.0 M aqueous hydrochloric acid solution, and the organic phase was concentrated under reduced pressure to give a yellow oily compound. Subsequently, the obtained oily compound was diluted with acetonitrile (60.0 g) and a 1.0 M aqueous hydrochloric acid solution (40.0 g), and reacted at 50 ° C. for 4 days. After completion of the reaction, the reaction was diluted with ethyl acetate, the aqueous hydrochloric acid phase was removed, and then the organic phase was washed 3 times with pure water. 1.0 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the recovered organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain a brown oily compound. Subsequently, acetonitrile was added and heated at 50 ° C. to obtain a uniform solution, ice-cooled to precipitate crystals, and filtration to obtain a crude product. The crude product was recrystallized from acetonitrile and tetrahydrofuran to obtain 10.1 g of MA-6 (yield: 37%, properties: white crystals).
^{1 1} H-NMR (400 MHz) in DMSO-d ₆ : 1.30-1.38 ppm (m, 4H), 1.57-1.87 ppm (m, 4H), 1.88 ppm (s, 3H), 2 .64ppm (t, 2H), 4.07ppm (t, 2H), 5.65-5.67ppm (m, 1H), 6.00-6.01ppm (m, 1H), 7.30-7.32ppm (M, 2H), 7.84-7.86ppm (m, 2H), 12.8ppm (s, 1H)
<Synthesis Example 4 Synthesis of MA-7>

<Synthesis of MA-7A>
MA-5A (49.0 g) was dissolved in methanol (98.8 g) and pure water (100.6 g), potassium hydroxide (14.8 g) was added, and the mixture was reacted under room temperature conditions for 2 hours. After completion of the reaction, ethyl acetate and a 3.0 M aqueous hydrochloric acid solution were added to acidify the aqueous phase side, and then the aqueous hydrochloric acid phase was removed. Subsequently, after washing the organic phase with pure water three times, 4.9 g of activated carbon (brand: specially made Shirasagi dried product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour, and then the activated carbon was removed by filtration. Then, it was concentrated under reduced pressure to obtain a crude MA-5B product. Subsequently, the obtained crude product was dissolved in tetrahydrofuran (119.1 g), and 5% palladium carbon powder (hydrous product) STD type (brand: N.E. Chemcat, Inc., 4.7 g) was charged, and 0.5 MPa hydrogen was added. The reaction was carried out under pressure conditions for 19 hours. After completion of the reaction, 27.7 g of MA-7A was obtained by filtering and washing the slurry with acetonitrile (three-step yield: 78%, properties: pale yellow crystals).

<Synthesis of MA-7>
MA-7A (26.1 g), triethylamine (30.3 g) and N, N-dimethyl-4-aminopyridine (0.71 g) were charged in tetrahydrofuran (166.7 g) under ice-cooled conditions in a nitrogen atmosphere. Methacryloyl chloride (28.3 g) was added dropwise and reacted under room temperature conditions for 2 hours. After completion of the reaction, the mixture was diluted with ethyl acetate, washed once with a 1.0 M aqueous hydrochloric acid solution and once with pure water, and the organic phase was concentrated under reduced pressure to give a yellow oily compound. Subsequently, the obtained oily compound was diluted with acetonitrile (72.4 g) and a 1.0 M aqueous hydrochloric acid solution (52.0 g), and reacted at 50 ° C. for 4 days. After completion of the reaction, the reaction was diluted with ethyl acetate, the aqueous hydrochloric acid phase was removed, and then the organic phase was washed 3 times with pure water. 1.3 g of activated carbon (brand: specially made dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the recovered organic phase, and the mixture was stirred under room temperature conditions for 1 hour, filtered, and concentrated under reduced pressure to obtain a brown oily compound. Subsequently, acetonitrile was added and heated at 50 ° C. to obtain a uniform solution, ice-cooled to precipitate crystals, and filtration to obtain a crude product. The crude product was recrystallized from acetonitrile and tetrahydrofuran to obtain 5.3 g of MA-7 (yield: 16%, properties: white crystals).
^{1 1} H-NMR (400 MHz) in DMSO-d ₆ : 1.27-1.31 ppm (m, 6H), 1.54-1.62 ppm (m, 4H), 1.88 ppm (s, 3H), 2 .63ppm (t, 2H), 4.08ppm (t, 2H), 5.65-5.67ppm (m, 1H), 6.00-6.01ppm (m, 1H), 7.30-7.32ppm (M, 2H), 7.84-7.87 ppm (m, 2H), 12.8 ppm (s, 1H)
<Synthesis Example 5 Synthesis of MA-8>

<Synthesis of MA-8A>
Propargyl alcohol (200.5 g) and pyridinium p-toluenesulfonate (44.9 g) were charged in methylene chloride (802.0 g), and 3,4-dihydro-2H-pyran (361) was charged under ice-cooled conditions in a nitrogen atmosphere. .7 g) was added dropwise. After the dropping, the reaction was carried out at room temperature for 5 hours. After completion of the reaction, the organic phase was washed 3 times with pure water, dehydrated with magnesium sulfate, and concentrated under reduced pressure to obtain 522 g of a crude product of MA-8A (crude yield: 104%, properties: light yellow oil). State compound).

<Synthesis of MA-8B>
In toluene (500.0 g), 1-bromo-4-iodobenzene (100.0 g) and piperidine (60.1 g), copper iodide (4.04 g), bis (triphenylphosphine) palladium (II) dichloride ( 7.44 g) was charged and stirred for 2 minutes in a nitrogen atmosphere. Subsequently, MA-8A (69.4 g) was added dropwise over 30 minutes. Since the reaction temperature rose sharply during the dropping, the dropping operation was carried out so that the temperature was about 23 ° C. after cooling with water. After completion of the dropping, stirring was poor, so toluene (500.0 g) was added and the reaction was carried out for 1 hour. After completion of the reaction, the organic phase was washed once with pure water, once with a 1.0 M aqueous hydrochloric acid solution, and again with pure water four times to recover the organic phase. Subsequently, 10.0 g of activated carbon (brand: special dried Shirasagi product manufactured by Japan Enviro Chemicals) was added to the recovered organic phase, stirred for 1 hour, filtered, and concentrated under reduced pressure to obtain 118.2 g of a crude product of MA-8B. (Crude yield: 113%, Properties: Blackish brown oily compound).

<Synthesis of MA-8C>
4-Hydroxyphenylboronic acid pinacol ester (60.1 g) and MA-8B (92.6 g), cesium carbonate (179.8 g) in N, N-dimethylformamide (300.5 g) and pure water (120.2 g). ) Was charged, tri-ter-butylphosphine (3.70 g) and bis (triphenylphosphine) palladium (II) dichloride (5.75 g) were added in a nitrogen atmosphere, and the mixture was reacted at 60 ° C. for 7 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and washed once with 1.0 M aqueous hydrochloric acid solution and three times with pure water. To the recovered organic phase, 6.0 g of activated carbon (brand: special dried Shirasagi product manufactured by Japan Enviro Chemicals) was added, stirred for 1 hour, filtered, and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column (hexane: ethyl acetate = 6: 1 volume ratio) to obtain 60.2 g of MA-8C (yield: 72%, properties: light orange crystals).

<Synthesis of MA-8D>
MA-8C (42.0 g) and 5% palladium carbon powder (hydrous product) STD type (brand: N.E. Chemcat, Inc., 3.36 g) were charged in tetrahydrofuran (120.3 g), and 0.4 MPa hydrogen pressure condition was applied. Was reacted for 28 hours. After completion of the reaction, the mixture was filtered and concentrated under reduced pressure. The obtained crude product was purified by silica gel column (hexane: ethyl acetate = 6: 1 volume ratio) to obtain 29.0 g of MA-8D (yield: 68%, properties: pale yellow oily compound).

<Synthesis of MA-8E>
MA-8D (25.0 g) and 4-methoxyxic carbodiimide (15.0 g), N, N-dimethyl-4-aminopyridine (1.00 g), 1-ethyl-3-3 in tetrahydrofuran (124.8 g). (3-Dimethylaminopropyl) carbodiimide hydrochloride (18.4 g) was charged and reacted under nitrogen atmosphere room temperature conditions for 18 hours. After completion of the reaction, the reaction solution was poured into pure water to obtain a crude reaction product. The obtained crude product was slurry-washed with 2-propanol to obtain 34.8 g of MA-8E (yield: 92%, properties: white crystals).

<Synthesis of MA-8F>
MA-8E (34.8 g) and pyridinium p-toluenesulfonate (3.70 g) were charged in ethanol (278.0 g) and reacted at 70 ° C. for 21 hours. After completion of the reaction, the reaction solution was poured into pure water to obtain a crude reaction product. Subsequently, the obtained crude product was subjected to slurry washing with methanol and recrystallized from tetrahydrofuran and methanol to obtain 25.7 g of MA-8F (yield: 90%, properties: white crystals).

<Synthesis of MA-8>
MA-8F (25.1 g) and triethylamine (8.52 g) were charged in tetrahydrofuran (278.4 g), and methacryloyl chloride (8.30 g) was added dropwise under ice-cooled conditions in a nitrogen atmosphere. After completion of the dropping, the reaction was carried out at room temperature for 20 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate under the condition of 45 ° C., washed with pure water three times, and concentrated under reduced pressure to obtain a crude product. The obtained crude product was redissolved in tetrahydrofuran, 2.5 g of activated carbon (brand: special dried Shirasagi product manufactured by Japan Enviro Chemicals) was added, and the mixture was stirred under room temperature conditions for 1 hour and then filtered. Subsequently, the obtained solution was concentrated under reduced pressure to bring the total internal weight to 151.4 g, and then methanol was added to precipitate crystals. The obtained crystals were slurry-washed with ethyl acetate, filtered, and dried to obtain 15.2 g of MA-8 (yield: 51%, properties: pale yellow crystals).
^{1 1} H-NMR (400 MHz) in CDCl ₃ : 1.95 ppm (s, 3H), 2.03-2.08 ppm (m, 2H), 2.78 ppm (t, 2H), 3.84 ppm (s, 3H) ), 4.20 ppm (t, 2H), 5.56 ppm (s, 1H), 6.11 ppm (s, 1H), 6.52 ppm (d, 1H), 6.92-6.96 ppm (m, 2H) , 7.21-7,27 ppm (m, 4H), 7.49-7.61 ppm (m, 6H), 7.85 ppm (d, 1H).

The abbreviations of the organic solvents used in the examples and the like are as follows.
NMP: N-methyl-2-pyrrolidone BC: Ethylene glycol monobutyl ether THF: tetrahydrofuran PGME: 1-methoxy-2-propanol

<Measurement of molecular weight of polymer>
The molecular weight of the (meth) acrylic polymer in the examples was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. It was measured in this way.
Column temperature: 50 ° C
Eluent: DMF (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) is 30 mmol / L, THF is 10 mL / L)
Flow velocity: 1.0 mL / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratory (molecular weight: about 900,000, 150,000, 100,000, 30,000). Molecular weight of about 12,000, 4,000, 1,000).

<Polymerization example 1>
MA-1 (13.3 g, 40.0 mmol) and MA-2 (18.4 g, 60.0 mmo)
l) was dissolved in THF (182.3 g), degassed with a diaphragm pump, and then 2
, 2'-Azobisisobutyronitrile (0.82 g, 5.0 mmol) was added, and degassing was performed again. Then, the reaction was carried out at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. The polymer solution was added dropwise to diethyl ether (1500 ml) and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder (P1). The number average molecular weight of this polymer was 35,000 and the weight average molecular weight was 126,000.

<Polymerization example 2>
MA-1 (1.19 g, 3.6 mmol), MA-2 (0.83 g, 2.7 mmol) and MA-4 (0.77 g, 2.7 mmol) were dissolved in THF (11.4 g). After degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 142 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 2.1 g (P2) of methacrylate polymer powder. The polymer had a number average molecular weight of 54,000 and a weight average molecular weight of 100,000.

<Polymerization example 3>
MA-1 (1.20 g, 3.6 mmol), MA-2 (0.83 g, 2.7 mmol) and MA-5 (0.81 g, 2.7 mmol) were dissolved in THF (11.5 g). After degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 144 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 2.1 g of methacrylate polymer powder. The number average molecular weight of this polymer was 50,000 and the weight average molecular weight was 100,000.

<Polymerization example 4>
MA-1 (1.20 g, 3.6 mmol), MA-2 (0.83 g, 2.7 mmol) and MA-6 (0.78 g, 2.7 mmol) were dissolved in THF (11.4 g). After degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 143 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 2.0 g (P4) of methacrylate polymer powder. The polymer had a number average molecular weight of 49000 and a weight average molecular weight of 100,000.

<Polymerization example 5>
MA-1 (0.80 g, 2.4 mmol), MA-2 (0.55 g, 1.8 mmol) and MA-7 (0.54 g, 1.8 mmol) were dissolved in THF (7.7 g). After degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.030 g, 0.18 mmol) was added and degassed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 96 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 1.4 g (P5) of methacrylate polymer powder. The number average molecular weight of this polymer was 38,000 and the weight average molecular weight was 90,000.

<Polymerization example 6>
MA-3 (2.0 g, 6.9 mmol) was dissolved in THF (11.7 g), degassed with a diaphragm pump, and then 2,2'-azobisisobutyronitrile (0.035 g) was added. , 0.21 mmol) was added and degassing was performed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 103 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 1.4 g (P6) of methacrylate polymer powder. The number average molecular weight of this polymer was 35,000 and the weight average molecular weight was 65,000.

<Polymerization example 7>
MA-4 (1.0 g, 3.5 mmol) was dissolved in THF (4.1 g), degassed with a diaphragm pump, and then 2,2'-azobisisobutyronitrile (0.017 g). , 0.10 mmol) was added and degassing was performed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 51 g of acetonitrile, and the obtained precipitate was filtered. The precipitate was washed with acetonitrile and dried under reduced pressure in an oven at 50 ° C. to obtain 0.5 g (P7) of methacrylate polymer powder. The number average molecular weight of this polymer was 35,000 and the weight average molecular weight was 68,000.

<Polymerization Example 8>
MA-6 (0.99 g, 3.4 mmol) was dissolved in THF (4.0 g), degassed with a diaphragm pump, and then 2,2'-azobisisobutyronitrile (0.017 g). , 0.10 mmol) was added and degassing was performed again. Then, the reaction was carried out at 60 ° C. for 13 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 50 g of acetonitrile, and the resulting precipitate was filtered. The precipitate was washed with acetonitrile and dried under reduced pressure in an oven at 50 ° C. to obtain 0.6 g (P8) of methacrylate polymer powder. The polymer had a number average molecular weight of 38,000 and a weight average molecular weight of 74,000.

<Polymerization example 9>
MA-8 (2.05 g, 4.5 mmol) was dissolved in THF (18.7 g), degassed with a diaphragm pump, and then 2,2'-azobisisobutyronitrile (0.022 g) was added. , 0.13 mmol) was added and degassing was performed again. Then, the reaction was carried out at 60 ° C. for 14 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to 208 g of methanol, and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 50 ° C. to obtain 1.4 g (P9) of methacrylate polymer powder. The number average molecular weight of this polymer was 33000 and the weight average molecular weight was 48,000.

<Polymerization Example 10>
The methacrylate polymer (P10) of MA-9 was synthesized by the synthetic method described in Patent Document (Japanese Patent Laid-Open No. 2006-308878).

<Solubility test>
<Example 1>
NMP (0.47 g) was added to 0.2 g of the obtained methacrylate polymer powder (P2), and the mixture was dissolved by stirring at room temperature for 12 hours. BC (7.0 g) was added to this solution and polymer solubility was confirmed.
<Examples 2 to 4, Comparative Example 1>
The polymer solubility of Examples 2 to 4 was confirmed using the same method as in Example 1. In addition, the polymer solubility of Comparative Example 1 was confirmed by the same method. The results are shown in Table 1.

<Solubility test>
<Example 5>
PGME (0.45 g) was added to 0.05 g of the obtained methacrylate polymer powder (P7), and the mixture was stirred at room temperature for 12 hours to confirm polymer solubility.
<Example 6>
PGME (0.45 g) was added to 0.05 g of the obtained methacrylate polymer powder (P8), and the mixture was stirred at room temperature for 12 hours to confirm polymer solubility.
<Comparative example 2>
PGME (0.45 g) was added to 0.05 g of the obtained methacrylate polymer powder (P6), and the mixture was stirred at room temperature for 12 hours to confirm polymer solubility.
Table 2 shows the solubility test results of Examples 5 and 6 and Comparative Example 2.

<Solubility test>
<Example 7>
NMP (0.96 g) was added to 0.05 g of the obtained methacrylate polymer powder (P9), and the mixture was dissolved by stirring at room temperature for 12 hours. BC (0.24 g) was added to this solution to confirm polymer solubility.

<Comparative example 3>
NMP (0.96 g) was added to 0.05 g of the obtained methacrylate polymer powder (P10), and the mixture was dissolved by stirring at room temperature for 12 hours. BC (0.24 g) was added to this solution to confirm polymer solubility.
The solubility test results of Example 7 and Comparative Example 3 are shown in Table 3.

As shown in Tables 1, 2 and 3, the polymer obtained by homopolymerizing and copolymerizing the polymerizable compound (MA-4 to MA-8) in which the linking group of the present invention is a single bond or a triple bond is a conventional ether bond. It was confirmed that the solubility in BC and PGME was improved as compared with the polymer obtained by homopolymerizing and copolymerizing the type polymerizable compounds (MA-1 to MA-3, MA-9). Therefore, it was suggested that the solvent selectivity could be expanded by using a polymer obtained by homopolymerization or copolymerization of an acrylic monomer having a single bond or a triple bond as a bonding group.

<Preparation of liquid crystal alignment agent>
<Example 8>
NMP (7.6 g) was added to 0.4 g of the obtained taclilate polymer powder (P2), and the mixture was dissolved by stirring at room temperature for 3 hours. BC (2.0 g) was added to this solution and stirred to obtain a liquid crystal alignment agent (A-1).

<Example 9>
NMP (7.6 g) was added to 0.4 g of the obtained taclilate polymer powder (P3), and the mixture was dissolved by stirring at room temperature for 3 hours. BC (2.0 g) was added to this solution and stirred to obtain a liquid crystal alignment agent (A-2).

<Example 10>
NMP (7.6 g) was added to 0.4 g of the obtained taclilate polymer powder (P4), and the mixture was dissolved by stirring at room temperature for 3 hours. BC (2.0 g) was added to this solution and stirred to obtain a liquid crystal alignment agent (A-3).

<Example 11>
NMP (7.6 g) was added to 0.4 g of the obtained taclilate polymer powder (P5), and the mixture was dissolved by stirring at room temperature for 3 hours. BC (2.0 g) was added to this solution and stirred to obtain a liquid crystal alignment agent (A-4).

<Example 12>
Chloroform (9.8 g) was added to 0.2 g of the obtained taclilate polymer powder (P9), and the mixture was stirred and dissolved at room temperature for 3 hours to obtain a liquid crystal alignment agent (A-5).

<Creation of board for order parameter measurement>
<Example 13>
Using the liquid crystal alignment agent (A-1) obtained in Example 8, a substrate for order parameter measurement was produced by the procedure as shown below. As the substrate, a quartz substrate having a size of 40 mm × 40 mm and a thickness of 1.0 mm was used.
The liquid crystal alignment agent (A-1) obtained in Example 8 is filtered through a 1.0 μm filter, spin-coated on a quartz substrate, dried on a hot plate at 70 ° C. for 90 seconds, and then has a film thickness of 100 nm. A liquid crystal alignment film was formed. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm at 5 to 50 mJ / cm ² via a polarizing plate, and then heated on a hot plate at 140 ° C. to 160 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.

<Examples 14 to 16>
For the liquid crystal alignment agents (A-2 to A-4) obtained in Examples 9 to 11, order parameter measurement substrates were prepared using the same method as in A-1.

<Example 17>
Using the liquid crystal alignment agent (A-5) obtained in Example 12, a substrate for order parameter measurement was produced by the procedure as shown below. As the substrate, a quartz substrate having a size of 40 mm × 40 mm and a thickness of 1.0 mm was used.
The liquid crystal alignment agent (A-5) obtained in Example 12 is filtered through a 1.0 μm filter, spin-coated on a quartz substrate, dried on a hot plate at 70 ° C. for 90 seconds, and then has a film thickness of 200 nm. A liquid crystal alignment film was formed. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm at 50 to 1000 mJ / cm ² via a polarizing plate, and then heated on a hot plate at 170 ° C. to 230 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.

<Measurement of order parameters>
Using the substrate with the liquid crystal alignment film prepared above, in order to measure the optical anisotropy of the liquid crystal alignment film, S, which is an order parameter, was calculated from the absorbance of polarized light from the following formula.

Here, A _para represents the absorbance in the direction parallel to the irradiated polarized UV direction, and A _per represents the absorbance in the direction perpendicular to the irradiated polarized UV direction. A _large is parallel and vertical absorbance absorbance having a larger value than the, A _small represents towards absorbance value is small compared to parallel and vertical directions of the absorbance. The closer the absolute value [S] of the in-plane orientation is to 1, the more uniform the orientation is. The order parameter indicates that the closer to 1 or -1, the more uniform the orientation state.
The calculated absolute value [S] of the order parameter is shown in Tables 4 and 5. The absolute value of the order parameter is shown according to the following criteria.
◯: 0.5 or more ○ △: 0.4 or more and less than 0.5 Δ: 0.3 or more and less than 0.4 ×: less than 0.3 A near-infrared analysis photometer U-3100PC was used.

As shown in Tables 4 and 5, liquid crystal aligning agents A1 to A4 and polymers P9 containing polymers P2 to P5 copolymerized with a polymerizable compound (MA4 to MA7) in which the linking group of the present invention is a single bond or a triple bond are used. The liquid crystal aligning agent A5 contained had an order parameter value of about 0.5 to 0.4, and it was confirmed that the liquid crystal aligning agent A5 functions as a liquid crystal alignment film.

Claims (9)

In the polymer composition containing (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a temperature range of 100 ° C. to 300 ° C. and (B) an organic solvent, the resin as the component (A) is used. The following formula (a)
(In the formula (a), L is a linear or branched alkylene having 1 to 16 carbon atoms.
X represents CH _{2 -CH 2} , CH = CH or C≡C.
Y ¹ is independently a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a dialkylamino group. (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. or branched-chain acyl group, a carboxyl group, a Y ¹ -6 from a good formula Y ¹ -1 be substituted with a substituent selected from an aldehyde group and a nitro group (** represents a bonding position to X , *** represents the position of connection with ^{Y 2).}
Y ² represents -COOH, -CR ³ = CR ^4- COOH, -CR ⁵ = CR ^6- CO-O-Y ³ or -O-CO-CR ⁵ = CR ^6- Y ³ .
R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively.
R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively.
Y ³ are each independently a halogen group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a dialkylamino group (The alkyl groups are independently linear or branched alkyl groups having 1 to 10 carbon atoms), linear or branched ester groups having 1 to 10 carbon atoms, and linear chains having 1 to 10 carbon atoms. Alternatively, a phenyl group, a biphenyl group, a naphthyl group, an alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl- which may be substituted with a substituent selected from an acyl group, a carboxyl group, an aldehyde group and a nitro group of the branched chain. Represents a cyclohexyl group or a cyclohexyl-phenyl group. )
A polymer composition comprising a side chain represented by.

The composition according to claim 1, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries rearrangement. The component (A) is the following formulas (1) to (6).
(In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, 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. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
The composition according to claim 1 or 2, which has any one of the photosensitive side chains selected from the group consisting of.

The component (A) is the following formulas (21) to (31).
(In the formula, A and B have the same definition as above;
Y ₃ is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and, with a group selected from the group consisting of Yes, the hydrogen atoms attached to them may be independently _{substituted with -NO 2} , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ contains 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, and nitrogen. Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the sum of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers 1 to 3;
R ₂ is 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 having 5 to 8 carbon atoms. And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ represent single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- )
The composition according to any one of claims 1 to 3, which has any one liquid crystal side chain selected from the group consisting of.

[I] A step of applying the composition according to any one of claims 1 to 4 onto a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III] [II];
A method for manufacturing a substrate having the liquid crystal alignment film, which obtains a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which the orientation control ability is imparted. A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method according to claim 5. A transverse electric field driven liquid crystal display element having the substrate according to claim 6. A step of preparing the substrate (first substrate) according to claim 6;
[I'] A step of applying the polymer composition according to any one of claims 1 to 17 on a second substrate to form a coating film;
[II'] A step of irradiating the coating film obtained in [I'] with polarized ultraviolet rays; and a step of heating the coating film obtained in [III'] [II'];
A step of obtaining a second substrate having the liquid crystal alignment film, which obtains a liquid crystal alignment film to which the orientation control ability is imparted by having the liquid crystal alignment film; A step of arranging the first and second substrates so as to face each other so that the films face each other to obtain a liquid crystal display element;
A method for manufacturing a liquid crystal display element, which obtains a horizontal electric field drive type liquid crystal display element. A transverse electric field driven liquid crystal display element manufactured by the method according to claim 8.