TW201811838A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and novel monomer - Google Patents

Abstract

Provided are a novel polymer composition for obtaining a liquid crystal alignment film, a liquid crystal alignment film which uses the same, and a novel monomer. The present invention provides a polymer composition containing (A) a photosensitive-side-chain-type polymer exhibiting liquid crystal properties in a predetermined temperature range, and (B) an organic solvent, wherein the polymer composition is characterized in that a resin as component (A) contains a side chain represented by formula (a). (In formula (a): L is a C1-16 straight-chain or branched-chain alkylene; X represents CH2-CH2, CH=CH, or C≡C; Y1 each independently represents a phenylene group or the like; Y2 represents -COOH, -CR3=CR4-COOH, -CR5=CR6-CO-O-Y3, or -O-CO-CR5=CR6-Y3; R3, R4, R5, and R6 each independently represents a hydrogen atom or a methyl group, and Y3 represents a phenyl group or the like).

Description

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

The present invention relates to a novel polymer having a specific structural unit, a composition containing the same (liquid crystal alignment agent), a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element using the same, and a substrate having the alignment film. Production method.

Liquid crystal display elements are known as light-weight, thin, and low-power-consumption display devices. In recent years, they have been significantly used for large-scale television applications. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In addition, in a liquid crystal display element, an organic film made of an organic material can be used as the liquid crystal alignment film so that the liquid crystal is brought into a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on a surface where the substrate holding the liquid crystal and the liquid crystal are in contact with each other, and serves to orient the liquid crystal in a certain direction between the substrates. In addition, the liquid crystal alignment film is required not only to perform a function of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate, but also to function as a pretilt angle of the liquid crystal. The ability to control the alignment of liquid crystals in such a liquid crystal alignment film (hereinafter referred to as alignment control ability) can be imparted by performing an alignment treatment on an organic film constituting the liquid crystal alignment film.

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

However, the friction method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generation of dust or static electricity. In addition, in recent years, due to the high definition of liquid crystal display elements, or unevenness caused by electrodes on corresponding substrates or active switching elements for liquid crystal driving, the surface of the liquid crystal alignment film may not be uniformly rubbed with cloth, and Uniform alignment of the liquid crystal cannot be achieved.

Therefore, as another alignment processing method for a liquid crystal alignment film that cannot be rubbed, a photo-alignment method is being actively reviewed.

There are various methods of photo-alignment. 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 aligned according to the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. In this method, for example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by using the polarization direction dependence of ultraviolet absorption of a molecular structure. In addition, the liquid crystal is aligned with polyfluorene imide remaining without being decomposed (for example, refer to Patent Document 1).

As another photo-alignment method, a photo-crosslinking type or a photo-isomerization type photo-alignment method is also known. In the photo-crosslinking type photo-alignment method, for example, polyvinyl cinnamate is used, and polarized ultraviolet rays are irradiated to cause a dimerization reaction (cross-linking reaction) in the double bond portion of two side chains parallel to the polarized light. In addition, the liquid crystal is aligned in a direction orthogonal to the polarization direction (for example, refer to Non-Patent Document 1). In the photo-isomerization type photo-alignment method, when a side-chain type polymer having azobenzene in a side chain is used, polarized ultraviolet light is irradiated to cause isomerization of an azobenzene portion of a side chain parallel to the polarized light. In response, the liquid crystal is aligned in a direction orthogonal to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, in the alignment processing method of the liquid crystal alignment film by the photo-alignment method, there is no need for friction, and there is no fear of generation of dust or static electricity. In addition, even a substrate of a liquid crystal display element having an uneven surface can be subjected to an alignment treatment, which will become an alignment treatment method of a liquid crystal alignment film suitable for an industrial production process.

In addition, as a photo-alignment polymer, a liquid crystal alignment agent using a photo-reactive polymer exhibiting liquid crystallinity in a specified temperature range has also been proposed.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent No. 3893659

[Patent Document 2] International Patent Application Publication No. WO2014 / 054785

    [Non-patent literature]    

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

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

However, when a photoreactive polymer that exhibits liquid crystallinity in a specified temperature range is used as the photo-alignment polymer, the solubility of the polymer may be reduced, which may be impractical. Therefore, a polymer having a high solubility is required while introducing various structures.

The present inventors have discovered that by introducing a specific structural unit into a photo-alignable polymer, the solubility of the polymer can be improved. That is, an object of the present invention is to provide a photoreactive polymer into which a specific structural unit capable of improving the solubility of a polymer is introduced, and a liquid crystal alignment agent containing the same. A novel monomer for introducing the specific structural unit is also provided.

As a result of intensive studies to achieve the above-mentioned problems, the inventors have found the following inventions.

<1>. A polymer composition characterized in that the polymer composition contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specified temperature range, and (B) an organic solvent The resin of the component (A) contains a side chain represented by the following formula (a). In particular, a polymer composition for manufacturing a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element.

In the formula (a), L is a linear or branched alkylene group having 1 to 16 carbon atoms.

X represents CH ₂ -CH ₂ , CH = CH or C≡C.

Y ¹ each independently represents 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, hydroxyl group, cyano group, Alkylamino groups (alkyl groups are each independently a straight or branched alkyl group having 1 to 10 carbon atoms), a straight or branched ester group having 1 to 10 carbon atoms, and a straight chain having 1 to 10 carbon atoms Or the branched fluorenyl, carboxyl, aldehyde and nitro substituents of the following formula Y ¹ -1 to Y ¹ -6 (** indicates the bonding position with X, *** indicates the Y ² bond position).

Y ² represents -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ^3, or -O-CO-CR ⁵ = CR ⁶ -Y ³ .

R ³ and R ⁴ are each independently represented as a hydrogen atom or a methyl group.

R ⁵ and R ⁶ are each independently represented as a hydrogen atom or a methyl group.

Y ³ is each independently selected from 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, Alkylamino groups (alkyl groups are each independently a straight or branched alkyl group having 1 to 10 carbon atoms), a straight or branched ester group having 1 to 10 carbon atoms, and a straight chain having 1 to 10 carbon atoms Or branched fluorenyl, carboxyl, aldehyde, and nitro substituents substituted with phenyl, biphenyl, naphthyl, 5-8 carbon alicyclic hydrocarbons, phenyl-cyclohexyl or cyclohexyl -Phenyl.

<2>. As in the above <1>, it is preferable that the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement.

<3>. As in said <1> or <2>, it is preferable that (A) component system has the photosensitive side chain chosen from the group which consists of any one of the following formula | equation (1)-(6).

In the formula, A, B, and D are independently represented as single bonds, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO- O-, or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to these may be replaced by a halogen group; T is a single bond or carbon number 1 ~ 12 alkylene, and the hydrogen atoms bonded to these may be replaced by halogen groups; Y ₁ represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and carbon number 5 to 8 rings of alicyclic hydrocarbons, or 2 to 6 rings of the same or different substituents selected from these substituents are groups bonded by a bonding group B, which is bonded to these The hydrogen atom system can be independently -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; Y ₂ is selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, Pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbons, and groups formed by combinations thereof. The hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, -CH = C ( CN) ₂ , -CH = CH-CN, halogen group, carbon number 1 ~ 5 alkyl group or alkoxy group having 1 to 5 carbon atoms; R represents a hydroxyl group, alkoxy group having 1 to 6 carbon atoms, or has the same definition as Y ₁ ; X represents a single bond,- COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, the number of X is At 2, X may be the same as or different from each other; the Cou system represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1, and the other One is 0; q3 is 0 or 1; P and Q are each 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 The base of the group formed by these combinations; however, if X is -CH = CH-CO-O-, -O-CO-CH = CH-, P on the -CH = CH- bonding side or Q is an aromatic ring. When the number of P is 2 or more, P may be the same or different; when the number of Q is 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is 0 ~ 2 Integer; when l1 and l2 are 0, A is also expressed when T is a single bond Single bond; when l1 is 1, B is also indicated as a single bond when T is a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and the like The basis of the combination.

<4>. As in any one of the above <1> to <3>, it is preferable that the component (A) has a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): .

In the formula, A and B have the same definitions as above; Y ₃ is selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, and alicyclic ring having 5 to 8 carbon atoms. Groups of formula hydrocarbons and combinations thereof, and the hydrogen atoms bonded to these groups may be independently -NO ₂ , -CN, halogen group, alkyl group having 1 to 5 carbon atoms, or carbon number 1 ~ 5 alkoxy group substituted; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, monovalent benzene ring, naphthalene ring , Biphenyl ring, furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; one of q1 and q2 Is 1 and the other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more. 25) to (26), the total of all m is 1 or more, m1, m2, and m3 are each independently expressed as an integer of 1 to 3; R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a heterocyclic ring containing nitrogen, carbon atoms, alicyclic hydrocarbon having 5 to 8, alkyl or alkoxy; Z _1, Z ₂ based table A single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 -.

<5>. A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is given: [I] Add the above <1 A step of applying a composition of any of> to <4> to a substrate having a conductive film for lateral electric field driving to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [ III] A step of heating the coating film obtained in [II].

<6>. A substrate comprising a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by the method of the above <5>.

<7>. A lateral electric field drive type liquid crystal display device having a substrate as described in <6> above.

<8>. A method for manufacturing a liquid crystal display element, which comprises obtaining a lateral electric field drive type liquid crystal display element by having the following steps: a step of preparing a substrate (first substrate) as in the above <6>; and obtaining a liquid crystal alignment The step of the second substrate of the film is to obtain the aforementioned liquid crystal alignment film provided with the alignment control ability by the following steps: [I '] Applying any of the above-mentioned <1> to <17> on the second substrate A step of forming a coating film with a polymer composition; [II '] a step of irradiating a polarized ultraviolet ray on the coating film obtained by [I']; and [III '] heating the coating film obtained by [II'] Step, and [IV] a step of obtaining a liquid crystal display element by arranging the first and second substrates oppositely so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween.

<9>. A lateral 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 represents a polymerizable group and is selected from polymerizable groups grouped by the following formulas PL-1 to PL-5. In the formulae PL-1 to PL-5, R ¹ , R ² , and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms substituted with halogen. A straight-chain or branched alkyl group (* indicates a bonding position with L).

L is a linear or branched alkylene group having 1 to 16 carbon atoms.

X represents CH ₂ -CH ₂ , CH = CH or C≡C.

Y ¹ is each independently selected from 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, Alkylamino groups (alkyl groups are each independently a straight or branched alkyl group having 1 to 10 carbon atoms), a straight or branched ester group having 1 to 10 carbon atoms, and a straight chain having 1 to 10 carbon atoms Or the branched fluorenyl, carboxyl, aldehyde and nitro substituents of the following formula Y ¹ -1 to Y ¹ -6 (** indicates the bonding position with X, *** indicates the Y ² bond position).

Y ² represents -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ^3, or -O-CO-CR ⁵ = CR ⁶ -Y ³ .

R ³ and R ⁴ are each independently represented as a hydrogen atom or a methyl group.

R ⁵ and R ⁶ are each independently represented as a hydrogen atom or a methyl group.

Y ³ is each independently selected from 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, Alkylamino groups (alkyl groups are each independently a straight or branched alkyl group having 1 to 10 carbon atoms), a straight or branched ester group having 1 to 10 carbon atoms, and a straight chain having 1 to 10 carbon atoms Or branched fluorenyl, carboxyl, aldehyde, and nitro substituents substituted with phenyl, biphenyl, naphthyl, 5-8 carbon alicyclic hydrocarbons, phenyl-cyclohexyl or cyclohexyl -Phenyl.

According to the present invention, a polymer having a specific structural unit can be obtained, and the obtained polymer system has improved solubility compared to conventional polymers. Accordingly, in order to realize various characteristics required for the liquid crystal display element, when the structural unit is introduced, the introduction can be performed without worrying about a 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 lateral electric field drive type liquid crystal display element that provides alignment control ability with high efficiency and excellent burn-in characteristics, and a lateral electric field drive type liquid crystal display element having the substrate.

    [Best Mode for Implementing Invention]    

As a result of intensive research, the present inventors obtained the following findings and completed the present invention.

The polymer composition of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as a side chain polymer) capable of exhibiting liquid crystallinity, and a coating film system obtained by using the polymer composition has Film of a photosensitive side chain polymer exhibiting liquid crystallinity. This coating film does not need to be subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. In addition, after the polarized light irradiation, a coating film (hereinafter also referred to as a liquid crystal alignment film) provided with an alignment control ability is passed through a step of heating the side chain polymer film. At this time, the micro anisotropy exhibited by the polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is effectively re-aligned due to self-organization. As a result, an efficient alignment process can be achieved as a liquid crystal alignment film, and a liquid crystal alignment film to which a high alignment control ability is provided can be obtained.

In the polymer composition of the present invention, the side chain polymer of the component (A) contains a side chain represented by the formula (a). Accordingly, the solubility of the polymer composition in an organic solvent is improved. This phenomenon is considered to be that the polymer represented by the above formula (a) has a significantly improved interaction with polymers due to the effect of the linking group compared to a similarly structured polymer having a different linking group, and can be greatly improved. The desired effect. However, these lines contain the inventor's insights into the mechanism of the present invention and do not limit the present invention.

In addition, the polymer composition in the present invention may contain, as the component (C), a tetracarboxylic acid derivative and a diamine in addition to the organic solvent of the side chain polymer of the component (A) and the component (B). Polyamidic acid produced by compound polymerization, or polyimide produced by polyimidating polyamidic acid, polyurea produced by polymerizing a diisocyanate compound and a diamine compound, and A polyurea polyamidate produced by polymerizing an isocyanate compound with a tetracarboxylic acid derivative and a diamine compound, and a polyurea polyamidate produced by polyimidizing a polyurea polyamidate.

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

    <Polymer composition>    

A polymer composition is coated on a substrate having a conductive film for driving a lateral electric field, particularly a conductive film.

The polymer composition used in the production method of the present invention is characterized by containing (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specified temperature range, and (B) an organic solvent polymerization. In the composition, the resin of the component (A) contains a side chain represented by the following formula (a).

    << (A) side chain polymer >>    

(A) The component is a side chain polymer which exhibits liquid crystallinity and sensitivity in a predetermined temperature range.

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

(A) The side chain type polymer is preferably a photosensitive side chain having a reaction in light in a wavelength range of 250 nm to 400 nm.

(A) The side chain polymer is preferably a liquid crystal group (mesogenic group) exhibiting liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

(A) The side chain polymer-based main chain is bonded to a photosensitive side chain, and can induce a cross-linking reaction, an isomerization reaction, or a light Fries rearrangement by sensing light. The structure of the photosensitive side chain is not particularly limited, but a structure that induces a cross-linking reaction or light Fries rearrangement by sensing light is preferable, and a cross-linking reaction is more preferable. In this case, even if it is exposed to external stress such as heat, the achieved alignment 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 can satisfy such characteristics, but it is preferred that the side-chain structure has a rigid liquid crystal component. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structural system of this polymer can be made as follows: for example, it has a main chain and a side chain bonded thereto, and the side chain has biphenyl, terphenyl, phenylcyclohexyl, and phenylbenzoate groups , A liquid crystalline component such as azophenyl, and a photosensitive group that is bonded to the tip to cause a cross-linking reaction or an isomerization reaction by light induction; and has a main chain and a side chain bonded thereto, and The side chain has a phenylbenzoate group which is a mesogen component and causes a photo-Fries rearrangement reaction.

As a more specific example of the structure of a photosensitive side-chain polymer capable of exhibiting liquid crystallinity, a polymer having a main chain selected from the group consisting of (meth) acrylate, econate, fumarate, and maleic acid Free radically polymerizable groups such as esters, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and at least one of a group of siloxanes A structure in which the side chain is composed of at least one of the following formulae (1) to (6) is preferred.

In the formula, A, B, and D respectively represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -, Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to these can be replaced by a halogen group; T is a single bond or 1 to carbon number 12 is an alkylene group, and hydrogen atoms bonded thereto may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 The ring of ~ 8 alicyclic hydrocarbon, or the same or different 2 ~ 6 rings selected from these substituents is a group formed by a bonding group B, and is bonded to these hydrogens The atomic system can be independently -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH -CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms; Y ₂ is selected from bivalent benzene ring, naphthalene ring, biphenyl ring, furan ring, and pyrrole Rings, alicyclic hydrocarbons having 5 to 8 carbons, and groups formed by these combinations, and the hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, -CH = C (CN _{) 2, -CH = CH-CN} , a halogen group, having 1 to 5 carbon atoms, Alkyl or alkoxy having 1 to 5 substituted; R & lt line represents a hydroxyl, alkoxy having 1 to 6, or Y ₁ represents the same as defined above; X represents a single bond lines, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; the Cou series represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkoxy 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 each 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 the like The base of the group formed by combination; however, if X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is aromatic Ring, if the number of P is 2 or more, P may be the same or different; if the number of Q is 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0 ~ 2; When l1 and l2 are 0, A is also expressed when T is a single bond. When l1 is 1, B is also represented as a single bond when T is a single bond; H and I are each independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and the like The basis of the combination.

The side chain is preferably a photosensitive side chain selected from any one grouped by the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; L represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent Integer from 1 to 3; n is an integer from 0 to 12 (but B is a single bond when n = 0).

The side chain is preferably a photosensitive side chain selected from any one grouped by the following formulae (11) to (13).

In the formula, A, X, 1, m, m1, and R have the same definitions as described above.

The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , 1, 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 described 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 described above.

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

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 described above.

The (A) side chain polymer contains a side chain represented by the following formula (a).

In the formula (a), L is a linear or branched alkylene group having 1 to 16 carbon atoms.

X represents CH ₂ -CH ₂ , CH = CH or C≡C.

Y ¹ is each independently selected from 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 dioxane. Amino groups (alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms The following formula Y ¹ -1 to Y ¹ -6 substituted by the substituted fluorenyl, carboxyl, aldehyde and nitro substituents (** indicates the bonding position with X, *** indicates the bonding position with Y ² the bond position).

Y ² represents -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ^3, or -O-CO-CR ⁵ = CR ⁶ -Y ³ .

R ³ and R ⁴ are each independently represented as a hydrogen atom or a methyl group.

R ⁵ and R ⁶ are each independently represented as a hydrogen atom or a methyl group.

Y ³ is each independently selected from 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 dioxane. Amino groups (alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms Branched fluorenyl, carboxyl, aldehyde, and nitro substituents substituted with phenyl, biphenyl, naphthyl, 5-8 carbon alicyclic hydrocarbons, phenyl-cyclohexyl or cyclohexyl- Phenyl.

In addition, the (A) side chain type polymer preferably has a liquid crystal side chain selected from any one grouped by the following formulae (21) to (31).

In the formula, A, B, q1 and q2 have the same definitions as above; Y ₃ is selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a heterocyclic ring containing nitrogen, and a carbon number of 5 ~ 8 alicyclic hydrocarbons, and the groups formed by these combinations, and the hydrogen atoms bonded to these groups can be independently -NO ₂ , -CN, halogen groups, and 1 to 5 carbon alkyl groups. Or alkoxy with 1 to 5 carbon atoms; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, a monovalent Benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more. In formulas (25) to (26), The total of all m is 1 or more, and m1, m2, and m3 are independently represented by integers of 1 to 3. R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, and a naphthalene ring. , Biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group, or alkoxy group; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

    << Method for manufacturing photosensitive side chain polymer >>    

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

    [Photoreactive side chain monomer]    

The photoreactive side chain monomer refers to a monomer that can form a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.

As a photoreactive group which a side chain has, the following structure and its derivative are preferable.

As a more specific example of the photoreactive side chain monomer, it is selected from the group consisting of (meth) acrylate, econate, fumarate, maleate, α-methylene-γ- Free-radically polymerizable groups such as butyrolactone, styrene, vinyl, maleimide, norbornene, and at least one group consisting of siloxane, and a polymerizable group composed of the above formula (1 ) To (6) at least one type of photosensitive side chain (preferably, for example, the above-mentioned formula (7) to (10) at least one type of photosensitive side chain made of the above-mentioned formula (11) ~ The photosensitive side chain formed by at least one of (13), the photosensitive side chain represented by the above formula (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the above The structure of the photosensitive side chain represented by Formula (18) or (19) and the structure of the photosensitive side chain represented by Formula (20) described above is preferred.

    [Monomer having structural unit represented by 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 represents a polymerizable group and is selected from polymerizable groups grouped by the following formulas PL-1 to PL-5. In the formulae PL-1 to PL-5, R ¹ , R ² , and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms substituted with halogen. A straight-chain or branched alkyl group (* indicates a bonding position with L).

L is a linear or branched alkylene group having 1 to 16 carbon atoms.

X represents CH ₂ -CH ₂ , CH = CH or C≡C.

Y ¹ is each independently selected from 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 dioxane. Amino groups (alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms The following formula Y ¹ -1 to Y ¹ -6 substituted by the substituted fluorenyl, carboxyl, aldehyde and nitro substituents (** indicates the bonding position with X, *** indicates the bonding position with Y ² the bond position).

Y ² represents -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ^3, or -O-CO-CR ⁵ = CR ⁶ -Y ³ .

R ³ and R ⁴ are each independently represented as a hydrogen atom or a methyl group.

R ⁵ and R ⁶ are each independently represented as a hydrogen atom or a methyl group.

Y ³ is each independently selected from 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 dioxane. Amino groups (alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms Branched fluorenyl, carboxyl, aldehyde, and nitro substituents substituted with phenyl, biphenyl, naphthyl, 5-8 carbon alicyclic hydrocarbons, phenyl-cyclohexyl or cyclohexyl- Phenyl.

    << Manufacturing method of monomer am1 >>         [Manufacture of a terminal carboxylic acid monomer having a triple bond]    

Specific examples of the terminal carboxylic acid-type monomer (am1) having a triple bond include the following formulae (I-1) to (I-6).

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

These single systems are manufactured as follows. That is, an appropriate halogenated aryl derivative am1-1 and an alcohol am1-2 having a triple bond at the terminal are subjected to a gimmicky coupling reaction in the coexistence of a metal complex, a ligand, and a base. Coupling reaction to produce am1-3. Next, the obtained ester group of am1-3 was hydrolyzed to produce am1-4. Finally, am1-4 is reacted with propylene chloride or methacrylic acid chloride, and monomers (I-1) to (I ~ 6) having a triple bond can be produced by performing acid hydrolysis.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents hydrogen or methyl. The Ar system represents (Y ¹ -1) to (Y ¹ -6) of the expression (am1). Hal is a substituent having detachment ability, and for example, halogens such as F, Cl, Br, and I can be used; p-tosylate (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), methane sulfonate ( -OSO ₂ CH ₃ ), sulfonate group such as trifluoromethanesulfonate group (-OSO ₂ CF ₃ ), and the like. Among them, in terms of reactivity, Br, I, or a trifluoromethanesulfonate group is preferred. R is an alkylene group, preferably methyl or ethyl.

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

(am1-1-1) ~ (am1-1-3) are available from reagent companies.

(am1-1-4) can be synthesized by taking the patent document (WO 2010071335) as a reference.

(am1-1-5) is obtained by reacting (am1-1-5a) which can be synthesized from the literature (Bioorganic & Medicinal Chemistry Letters, 18 (15), 4339-4343; 2008) with trifluoromethanesulfonic anhydride. get.

(am1-1-6) is obtained by reacting (am1-1-6a) synthesized from a patent document (PCT Int. Appl., 2014113485) with trifluoromethanesulfonic anhydride.

In the reaction of am1-1 and am1-2, an appropriate metal complex and a ligand are used to form a metal complex catalyst and use it. Generally, a palladium complex or a nickel complex can be used as the metal complex, and it is preferable to coexist with a copper catalyst as a co-catalyst depending on the reaction.

As the metal complex catalyst, various structures can be used, and it is preferable to use a so-called low atomic valence palladium complex or nickel complex. Especially, a third-order phosphine or a third-order phosphite is used as a complex. A zero-valent metal complex catalyst is preferred. Moreover, an appropriate precursor that can be easily converted into a zero-valent metal complex catalyst can be used in the reaction system. Furthermore, in the reaction system, a metal complex containing no tertiary phosphine or tertiary phosphite as a ligand may be mixed with a tertiary phosphine or tertiary phosphite of a ligand to produce Low atomic valence metal complex catalyst using tertiary phosphine or tertiary phosphite as a ligand.

Examples of the tertiary phosphine or tertiary phosphite of the ligand include triphenylphosphine, tri-o-toluylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, and 1,2-bis (Diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) butane, 1,1'-bis (diphenylphosphine) dimene Iron, trimethyl phosphite, triethyl phosphite, triphenyl phosphite and the like. Metal complex catalysts containing two or more of these ligands are also suitable for use.

As the metal complex catalyst, a palladium complex containing no tertiary phosphine or a third phosphite and a metal complex containing a tertiary phosphine or a third phosphite are preferably used in combination. In this case, the above-mentioned ligands can be further combined. Examples of the palladium complex that does not contain a third-order phosphine or a third-order phosphite include bis (benzylideneacetone) palladium, ginsyl (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, and bis ( Benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. In addition, examples of the palladium complex containing a tertiary phosphine or a tertiary phosphite as a ligand include (ethylene) bis (triphenylphosphine) palladium, (triphenylphosphine) palladium, Bis (triphenylphosphine) dichloropalladium and the like.

The usage amount of these palladium complexes may be a so-called catalyst amount, and is preferably 20 mol% or less, and particularly preferably 10 mol% or less with respect to the compound am1-1. Meanwhile, the copper catalyst used as the promoter is preferably monovalent, and examples thereof include copper (I) chloride, copper (I) bromide, copper iodide (I), and copper acetate (I )Wait.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; methylamine, dimethyl Methylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine Methylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colin base, pyrrolidine, piperidine, morpholin, N-methyl Morpholine and other amines; sodium acetate, potassium acetate, lithium acetate, etc.

The reaction solvent can be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the reaction. As the reaction solvent, water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethylformamide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane Alkane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, n-benzene, tetrahydronaphthalene, etc.), halogen-based hydrocarbons (trichloromethane, dichloromethane, etc.) Methane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) )Wait. These solvents are appropriately selected in consideration of the easiness of causing the reaction, and may be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using an appropriate dehydrating agent or a desiccant.

The reaction temperature is preferably within a temperature range from -100 ° C or higher to the boiling point of the reaction solvent used, more preferably -50 to 200 ° C, and particularly preferably 20 to 150 ° C. The reaction time is 0.1 to 1000 hours, and more preferably 0.5 to 100 hours.

The compound am1-3 obtained by the above reaction is preferably purified by column chromatography such as distillation, recrystallization, or silica gel. The recrystallization system is preferably performed at a low temperature as much as possible.

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

    [Production of a 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 formulae (II-1) to (II-6).

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

In the formula (am1), when the compound am1 in which X is -CH ₂ -CH ₂ -is produced, the compound am1-4 is reduced, and after reacting with propylene chloride or methacrylic acid chloride, acid hydrolysis may be performed.

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

Examples of the method for reducing the compound am1-4 include a hydrogenation reaction using palladium-activated carbon or platinum-activated carbon as a catalyst, a reduction reaction in the coexistence of Fe, Sn, Zn, or a salt thereof and a proton, A reduction reaction using formic acid as a hydrogen source, a reaction using hydrazine as a hydrogen source, and the like. Moreover, these reactions can be combined and implemented.

Among the reduction reactions exemplified above, in consideration of the structure of the base compound am1-4 and the reactivity of the reduction reaction, it is preferable to use a hydrogenation reaction.

As the catalyst to be used, commercially available activated carbon-supporting metals include, for example, palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. In addition, palladium hydroxide, platinum oxide, Raleigh nickel, and the like do not necessarily need to be activated carbon-supported metal catalysts. Good results were obtained even with the widely used palladium-activated carbon.

As the reaction solvent, any solvent can be used as long as it is stable under the reaction conditions and is inert and does not hinder the intended reaction. Aprotic polar organic solvents such as dimethylformamide, dimethylmethane, dimethylacetate, N-methylpyrrolidone, etc. can be used; diethyl ether, isopropyl ether, THF , TBME, CPME, ethers such as dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether; benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nifediene, Aromatic hydrocarbons such as tetrahydronaphthalene, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc. Low-order fatty acid esters; nitriles such as acetonitrile, propionitrile, butyronitrile; alcohols such as methanol, ethanol, and 2-propanol.

These solvents may be appropriately selected in consideration of the easiness of reaction, and may be used alone or in combination of two or more. In addition, depending on the circumstances, an appropriate dehydrating agent or desiccant may be used as the solvent containing no water.

In order to allow the above reduction reaction to proceed more effectively, the reaction may be performed 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, and more preferably 1 to 10% by weight, based on the compound am1-4.

Furthermore, in order to advance the reaction more effectively, the reaction may be performed under pressure. In this case, in order to avoid reduction of benzene nuclei, the reaction is preferably performed in a pressure range of about 20 atmospheres (kgf), and more preferably in a range up to 10 atmospheres.

The reaction temperature is preferably within a temperature range from -100 ° C or higher to the temperature of the boiling point of the reaction solvent used, but is preferably -50 to 150 ° C, particularly preferably 0 to 80 ° C. The reaction time is 0.1 to 1000 hours, and more preferably 1 to 200 hours.

The compound am1-5 obtained by the above reduction reaction is preferably purified by column chromatography such as distillation, recrystallization, or silica gel.

The obtained compound am1-5 is reacted with propylene chloride or methacrylic acid chloride, and then hydrolyzed in a mixed solution of acetonitrile and hydrochloric acid to produce a compound (II-1) in which X is -CH ₂ -CH _2- . To (II-6).

    [Cinamic acid with three bonds. Manufacture of cinnamate type monomer]    

As a cinnamic acid with a triple bond. Specific examples of the cinnamate-type monomer (am1) include the following formulae (III-1) to (III-7).

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

These single systems are manufactured as follows. That is, an appropriate halogenated aryl derivative am1-6 and an alcohol am1-2 having a triple bond at the terminal are subjected to a gimmicky coupling reaction in the coexistence of a metal complex, a ligand, and a base. Coupling reaction to produce am1-7.

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. Make am1-9.

Finally, the obtained am1-9 is reacted with propylene chloride or methacrylic acid chloride and subjected to acid hydrolysis to produce monomers (III-1) to (III-5) having a triple bond.

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents hydrogen or methyl. The Ar system represents (Y ¹ -1) to (Y ¹ -6) of the expression (am1). Hal1 and Hal2 are substituents having detachability, and halogens such as F, Cl, Br, and I can be used; p-tosylate (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), methane sulfonate Group (-OSO ₂ CH ₃ ), sulfonate group such as trifluoromethanesulfonate group (-OSO ₂ CF ₃ ), and the like. Among them, in terms of reactivity, Br, I, or a trifluoromethanesulfonate group is preferred.

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

(am1-6-1) ~ (am1-6-3) are available from Reagent Company.

(am1-6-4) is obtained by reacting (am1-6-4a) synthesized from a patent document (Japanese Patent Application Laid-Open No. 2015-078153) with trifluoromethanesulfonic anhydride.

(am1-6-5) is obtained by reacting (am1-6-5a) which can be synthesized from a patent document (Japanese Patent Application Laid-Open No. 2015-078153) with trifluoromethanesulfonic anhydride.

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

In the reaction between am1-7 and tert-butyl acrylate (am1-8), an appropriate metal complex and a ligand are used to form a metal complex catalyst and use it. Generally, as the metal complex, a palladium complex or a nickel complex can be used.

As the metal complex catalyst, various structures can be used, and it is preferable to use a so-called low atomic valence palladium complex or nickel complex. Especially, a third-order phosphine or a third-order phosphite is used as a complex. A zero-valent metal complex catalyst is preferred. Moreover, an appropriate precursor that can be easily converted into a zero-valent metal complex catalyst can be used in the reaction system. Furthermore, in the reaction system, a metal complex containing no tertiary phosphine or tertiary phosphite as a ligand may be mixed with a tertiary phosphine or tertiary phosphite of a ligand to produce Low atomic valence metal complex catalyst using tertiary phosphine or tertiary phosphite as a ligand.

Examples of the tertiary phosphine or tertiary phosphite of the ligand include triphenylphosphine, tri-o-toluylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, and 1,2-bis (Diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) butane, 1,1'-bis (diphenylphosphine) dimene Iron, trimethyl phosphite, triethyl phosphite, triphenyl phosphite and the like. Metal complex catalysts containing two or more of these ligands are also suitable for use.

As the metal complex catalyst, it is also preferable to use a combination of a palladium complex containing no tertiary phosphine or tertiary phosphite and a metal complex containing tertiary phosphine or tertiary phosphite. In this case, the above-mentioned ligands can be further combined. Examples of the palladium complex that does not contain a third-order phosphine or a third-order phosphite include bis (benzylideneacetone) palladium, ginsyl (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, and bis ( Benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. In addition, examples of the palladium complex containing a tertiary phosphine or a tertiary phosphite as a ligand include (ethylene) bis (triphenylphosphine) palladium, (triphenylphosphine) palladium, Bis (triphenylphosphine) dichloropalladium and the like.

The usage amount of these palladium complexes may be a so-called catalyst amount, and is preferably 20 mol% or less, and particularly preferably 10 mol% or less with respect to the compound am1-1.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; methylamine, dimethyl Methylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine Methylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colin base, pyrrolidine, piperidine, morpholin, N-methyl Morpholine and other amines; sodium acetate, potassium acetate, lithium acetate, etc.

The reaction solvent can be used as long as it is stable under the reaction conditions and is inert so as not to hinder the reaction. As the reaction solvent, water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethylformamide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane Alkane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, n-benzene, tetrahydronaphthalene, etc.), halogen-based hydrocarbons (trichloromethane, dichloromethane, etc.) Methane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) )Wait. These solvents are appropriately selected in consideration of the easiness of causing the reaction, and may be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using an appropriate dehydrating agent or a desiccant.

The reaction temperature is preferably within a temperature range from -100 ° C or higher to the boiling point of the reaction solvent used, more preferably -50 to 200 ° C, and particularly preferably 20 to 150 ° C. The reaction time is 0.1 to 1000 hours, and more preferably 0.5 to 100 hours.

The compound am1-9 obtained by the above reaction is preferably purified by column chromatography such as distillation, recrystallization, or silica gel. The recrystallization system is preferably performed at a low temperature as much as possible.

Next, the obtained am1-9 is reacted with propylene chloride or methacrylic acid chloride in the presence of a base such as triethylamine, and acid hydrolysis is performed with formic acid to obtain (III-1) to (III-5).

After the compound (III-1) having a terminal of -CH = CHCOOH and tert-butyl 4-hydroxybenzoate are esterified with a condensing agent, etc., the terminal ester group is hydrolyzed with formic acid. , Can produce the compound (III-6) whose end is -CH = CH-COO-C ₆ H ₄ -COOH.

The obtained compound (III-1) having a terminal of -CH = CHCOOH and 4-methoxyphenol can be esterified with a condensing agent or the like to produce a terminal of -CH = CH-COO-C ₆ H _4- OMe compound (III-7).

    [Cinnamic acid with a single bond. Manufacture of cinnamate type monomer]    

As a cinnamic acid with a single bond. Specific examples of the cinnamate-type monomer (am1) include the following formulae (IV-1) to (IV-7).

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

When a compound in which X is -CH ₂ -CH ₂ -is produced, am1-11 can be produced by reducing the aforementioned compound am1-7.

By reacting the obtained am1-11 with am1-8 and Heck, am-1-12 can be produced. Next, after reacting with propylene chloride or methacrylic acid chloride, compounds (IV-1) to (IV-5) which are hydrolyzed by formic acid can be produced.

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

am1-11 can be manufactured by the same method as am1-5.

am1-12 can be manufactured by the same method as the synthesis method of am1-9.

In the presence of a base such as triethylamine, the obtained am1-12 is reacted with propylene chloride or methacrylic acid chloride, and acid hydrolysis is performed with formic acid to obtain (IV-1) to (IV- 5).

After the compound (IV-1) having a terminal of -CH = CHCOOH and tert-butyl 4-hydroxybenzoate are esterified with a condensing agent, etc., the terminal ester group is hydrolyzed with formic acid. , Can produce the compound (IV-6) whose terminal is -CH = CH-COO-C ₆ H ₄ -COOH.

The compound (IV-1) having a terminal of -CH = CHCOOH and 4-methoxyphenol can be esterified with a condensing agent and the like to produce a terminal of -CH = CH-COO-C ₆ H ₄ -OMe compound (IV-7).

    [Manufacture of non-carboxylic acid type monomer with triple bond]    

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

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

These single systems are manufactured as follows. That is, an appropriate halogenated aryl derivative am1-15 and an alcohol protector am1-14 having a triple bond at the terminal are co-existed in the presence of a metal complex, a ligand, and a base. Coupling reactions such as reactions to produce am1-16. In addition, am1-16 can be produced even by the combined steamed bun coupling reaction and Suzuki-Miyaura reaction.

Next, am1-18 can be produced by reacting am1-16 obtained with a cinnamic acid derivative (am1-17) in the presence of a condensing agent and a base.

Finally, the protecting group of am1-18 is deprotected and reacted with propylene chloride or methacrylic acid chloride in the presence of alkali to produce monomers (V-1) to (V-6) having triple bonds. ).

In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. R ¹ represents hydrogen or methyl. The Ar system represents (Y ¹ -1) to (Y ¹ -6) of the expression (am1). Ar ₁ represents a divalent organic group having an aromatic ring. Hal, Hal ₁ and Hal ₂ are substituents having detachability, and halogens such as F, Cl, Br, and I can be used; p-tosylate (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), Sulfonate groups such as a methanesulfonate group (-OSO ₂ CH ₃ ), trifluoromethanesulfonate group (-OSO ₂ CF ₃ ), and the like. Among them, in terms of reactivity, Br, I, or a trifluoromethanesulfonate group is preferred. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl. PG means a protecting group.

am1-14 is obtained by protecting the terminal alcohols of am1-2 through a suitable protecting group (PG). Examples of the type of the protecting group (PG) include protecting groups such as GREENE'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GMWUTS, THEODORA W. GREENE, A John Wiley & Sons, Inc., Publication) Is better. Particularly, protection using 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) ~ (am1-15-4) are available from reagent companies.

The am1-16 series can be manufactured using am1-15 as a raw material by the same method as the am1-3 synthesis method.

am1-16 uses am1-6 and am1-14 to obtain am1-16a by the same method as am1-3 synthesis method, and then uses the Suzuki-Miyaura reaction of organometallic reagent (am1-16b) and metal catalyst And available.

In the formula, Ar ₁ represents a divalent organic group having an aromatic ring. Hal is a substituent having detachment ability, and for example, halogens such as F, Cl, Br, and I can be used; p-tosylate (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), methane sulfonate ( -OSO ₂ CH ₃ ), sulfonate group such as trifluoromethanesulfonate group (-OSO ₂ CF ₃ ), and the like. Among them, in terms of reactivity, Br, I, or a trifluoromethanesulfonate group is preferred. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl. PG means a protecting group.

The aforementioned coupling reaction (Suzuki-Miyaura reaction) uses an appropriate metal complex and a ligand as a catalyst. Depending on the circumstances, the reaction proceeds even without a ligand. Generally, a palladium complex or a nickel complex can be used. As the catalyst, various structures can be used, and it is preferable to use a so-called low atomic valence palladium complex or nickel complex. In particular, zero valence using a third-order phosphine or a third-order phosphite as a ligand. A complex is preferred. Moreover, an appropriate precursor that can be easily converted into a zero-valent complex can be used in the reaction system. Further, in the reaction system, a complex containing no tertiary phosphine or tertiary phosphite as a ligand may be mixed with the tertiary phosphine or tertiary phosphite to generate a tertiary phosphine or tertiary phosphite. Low atomic valence complex of tertiary phosphite as a ligand. Examples of the tertiary phosphine or tertiary phosphite of the ligand include triphenylphosphine, tri- o -toluenephosphine, diphenylmethylphosphine, phenyldimethylphosphine, and 1,2-bis (Diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) butane, 1,1'-bis (diphenylphosphine) dimene Iron, trimethylphosphite, triethylphosphite, triphenylphosphite, and the like are also suitable for use as a metal complex catalyst containing two or more kinds of these ligands. As a catalyst, it is also preferable to use a combination of a palladium complex that does not contain a tertiary phosphine or a tertiary phosphite and a complex that contains a tertiary phosphine or a tertiary phosphite. Appearance. Examples of the complex which does not include a tertiary phosphine or a tertiary phosphite in combination with the above-mentioned ligands include bis (benzylideneacetone) palladium, ginsyl (benzylideneacetone) dipalladium, and bis ( (Acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, nickel chloride, nickel iodide, etc. Phosphine or tertiary phosphite complexes that are included as ligands include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, and Ethyl) bis (triphenylphosphine) fluorene, bis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1,3-bis (diphenylphosphine) propane] nickel (II) Dichloride, [1,2-bis (diphenylphosphine) ethane] nickel (II) dichloride, and the like are not limited to these. The amount of the palladium complex and nickel complex used may be a so-called catalyst amount, which is generally sufficient at 20 mol% or less with respect to the substrate, and usually 10 mol% or less.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate, or methylamines, Dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, trimethylamine In addition to amines such as isopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and collin base, sodium acetate, Potassium acetate, lithium acetate, etc.

As a solvent, those which are stable under the reaction conditions and are inert will not hinder the reaction. Can use 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, tetrahydronaphthalene Etc.), halogen-based hydrocarbons (trichloromethane, methylene chloride, carbon tetrachloride, dichloroethane, etc.), low-order fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.) Etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents may be appropriately selected in consideration of the ease of reaction, etc. In this case, the above solvents may 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, and more preferably 0.5 to 24 hours.

After the reaction, am1-16 obtained in the manner as described above can be purified by slurry washing, recrystallization, and silica gel column chromatography for purification.

In the reaction between am1-16 and 4-methoxycinnamic acid (am1-17), an appropriate condensing agent and a base are used. Examples of the condensing agent include N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethyl Aminopropyl) carbodiimide hydrochloride, N- [3- (dimethylamine) propyl] -N'-ethylcarbodiimide, N- [3- (dimethylamine ) Propyl] -N'-carbodiimide methyl iodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N '-(2-morpholinoethyl Carbodiimide-p-toluenesulfonate, N, N'-di-tert-butylcarbodiimide, N, N'-di-p-tolylcarbodiimide and other carbons Dihydrazone. Examples of the carbodiimide include triazine-based condensing agents, acid chlorides, acid anhydrides, and other condensing agents. As the base, for example, a primary amine, a secondary amine, a tertiary amine, or an aromatic amine and the amine salt can be used. In terms of yield, a tertiary amine or an aromatic amine and the amine salt can be used. Is better. Specific examples include 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-dipropyl Methylmethylamine, N, N-diethylpentylamine, N-ethyl-N-methylpentylamine, tributylamine, N, N-dibutylmethylamine, N, N-dibutyl Ethylamine, 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, acridine, N, N-dimethyl-4-aminopyridine, methylpyridine, bipyridine, 2,6-dimethylpyridine, pyridinium chlorochromate, pyridinium p-toluenesulfonate, and other tertiary or aromatic amines and the amine salt. Especially, N, N-dimethyl-4-aminopyridine is preferable.

The reaction solvent can be used as long as it is stable under the reaction conditions and is inert so as not to hinder the reaction. Aprotic polar organic solvents such as dimethylformamide, dimethylmethane, dimethylacetate, N-methylpyrrolidone, etc. can be used; diethyl ether, isopropyl ether, THF , TBME, CPME, ethers such as dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether; benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nifediene, Aromatic hydrocarbons such as tetrahydronaphthalene, halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, and dichloroethane; methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc. Low-order fatty acid esters; acetonitrile, propionitrile, butyronitrile, etc.

These solvents are appropriately selected in consideration of the easiness of causing the reaction, and may be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using an appropriate dehydrating agent or a desiccant.

The reaction temperature is preferably within a temperature range from -100 ° C or higher to the boiling point of the reaction solvent used, more preferably -50 to 200 ° C, and particularly preferably 20 to 150 ° C. The reaction time is 0.1 to 1000 hours, and more preferably 0.5 to 100 hours.

The compound am1-18 obtained by the above reaction is preferably purified by column chromatography such as distillation, recrystallization, or silica gel.

As the deprotection condition of the protecting group of am1-18, it is listed in GREENE'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GMWUTS, THEODORA W.GREENE, A John Wiley & Sons, Inc., Publication) The reaction conditions are better. In particular, it is preferable to use a catalytic amount of pyridinium p-toluenesulfonate for deprotection in ethanol.

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

    [Manufacture of non-carboxylic acid type monomer with single bond]    

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

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

When producing a compound in which X is -CH ₂ -CH _2- , am1-20 is produced by reducing the above compound am1-16, and then a condensation agent is used to perform a condensation reaction and a deprotection reaction with a cinnamic acid derivative. By reacting with propylene chloride or methacrylic acid chloride, (VI-1) to (VI-6) can be produced.

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

The am1-20 series can be manufactured by the same manufacturing method as the am1-5 synthesis method.

The am1-21 system can be manufactured by the same manufacturing method as the am1-18 synthesis method.

The am1-22 system can be manufactured by the same manufacturing method as the am1-19 synthesis method.

(VI-1) to (VI-6) can be obtained by reacting am1-22 with propylene chloride or methacrylic acid chloride in the presence of a base such as triethylamine.

    [Production of α-methylene-γ-butyrolactone monomer]    

Specific examples of the α-methylene-γ-butyrolactone-type monomer (am1) include the following formulae (VII-1) to (VII-6). In the formula, Q ¹ is a linear alkylene group having 1 to 16 carbon atoms. In the formula, Q ² is a linear alkylene group having 1 to 4 carbon atoms. R represents methyl and ethyl. Examples of R include a hydrogen atom and a C1-4 alkyl group. The Ar system represents (Y ¹ -1) to (Y ¹ -6) of the expression (am1).

The α-methylene-γ-butyrolactone compound (PL-2) can be synthesized by combining methods in organic synthetic chemistry, and the synthesis method is not particularly limited. Instead of am1-2 or am1-14, a halogenated alkane (am1-23) was introduced into am1-1, am1-6, or am1-15 by a steamed bun coupling reaction, and a known synthesis represented by the following formula was used. After conversion to acetal and ketal derivatives by manual methods, metal reagents and acrylic acid derivatives (am1-24) can be reacted under acidic conditions to synthesize (VII-1), (VII-2), and (VII- 5), (VII-6) (References: For example, P. Talaga, M. Schaeffer, C. Benezra and JLS tampf, Synthesis, 530 (1990)). In addition, the (VII-3) and (VII-4) systems can be synthesized by derivatizing them into α-methylene-γ-butyrolactone compounds, followed by acid hydrolysis with formic acid.

In the formula, Q ² is a linear alkylene group having 1 to 4 carbon atoms. R represents methyl and ethyl. Examples of R include a hydrogen atom and a C1-4 alkyl group. The Ar system represents (Y ¹ -1) to (Y ¹ -6) of the expression (am1). Hal, Hal ₁ , and Hal ₂ are substituents having detachability, and halogens such as F, Cl, Br, and I can be used; p-tosylate (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), Sulfonate groups such as a methanesulfonate group (-OSO ₂ CH ₃ ), trifluoromethanesulfonate group (-OSO ₂ CF ₃ ), and the like. Among them, in terms of reactivity, Br, I, or a trifluoromethanesulfonate group is preferred. Y is Cl or Br.

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

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

As a solvent, those which are stable under the reaction conditions and are inert will not hinder the reaction. Can use water, alcohols, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i -Pr ₂ O, TBME, CPME, tetrahydrofuran, dioxane, etc.), fats Hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nifediene, tetrahydronaphthalene, etc.), Halogen-based hydrocarbons (trichloromethane, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower-order fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), Nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents may be appropriately selected in consideration of the ease of reaction, etc. In this case, the above solvents may 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, and preferably 20 to 100 ° C. The reaction time is usually 0.05 to 200 hours, and preferably 0.5 to 60 hours.

After the reaction, the α-methylene-γ-butyrolactone compound obtained in the manner as described above can be prepared by slurry washing, recrystallization, and silica gel column chromatography. High purity.

The solvent used for washing is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane, and toluene, chloroform, halogen-based hydrocarbons such as 1,2-dichloroethane, and chlorobenzene, Diethyl ether, ether such as tetrahydrofuran or 1,4-dioxane, ester such as ethyl acetate, ketone such as acetone or methyl ethyl ketone, nitrile such as acetonitrile or propionitrile, methanol or Alcohols such as ethanol and 2-propanol, and mixtures thereof are preferably alcohols such as methanol or ethanol and 2-propanol.

The solvent used for recrystallization is not particularly limited as long as it is an α-methylene-γ-butyrolactone compound that can be dissolved upon heating and can be precipitated upon cooling, and examples thereof include hexane and heptane. Or hydrocarbons such as toluene, halogens such as chloroform, 1,2-dichloroethane, and chlorobenzene, ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, and ethyl acetate Esters such as esters, 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, preferably acetic acid Alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol, 2-propanol, hexane, or a mixture of these.

    [Liquid crystal side chain monomer]    

The liquid crystal side chain monomer refers to a monomer derived from a polymer of the monomer that can exhibit liquid crystallinity, and the polymer can form a liquid crystal group at a side chain site.

The liquid crystal group having a side chain may be a group having a liquid crystal structure alone such as biphenyl or phenyl benzoate, or a group having side chains such as benzoic acid and the like forming a liquid crystal structure through hydrogen bonding. The following structure is preferable as a liquid crystal group having a side chain.

As a more specific example of the liquid crystalline side chain monomer, it has a material selected from the group consisting of hydrocarbons, (meth) acrylates, econate, fumarate, maleate, α-methylene-γ- Free-radically polymerizable groups such as butyrolactone, styrene, vinyl, maleimide, norbornene, and at least one group consisting of siloxane, and a polymerizable group composed of the above formula (21 The structure of the side chain formed by at least one of () to (31) is preferable.

(A) The side chain type polymer system can be obtained by the above-mentioned polymerization reaction of a photoreactive side chain monomer exhibiting liquid crystallinity. In addition, it is possible to copolymerize a photoreactive side chain monomer and a liquid crystal side chain monomer which do not exhibit liquid crystallinity, or a photoreactive side chain monomer and a liquid crystal side chain monomer which exhibit liquid crystallinity. Available by copolymerization. Furthermore, it can copolymerize with other monomers in the range which does not impair the display ability of liquid crystallinity.

Examples of the other monomer include a commercially available monomer capable of performing a radical polymerization reaction.

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

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthryl methyl acrylate, phenyl acrylate, and acrylic acid 2,2,2 -Trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isoamyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-triacrylate Cyclodecyl ester, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and methyl Anthryl methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isoamyl methacrylate, methyl 2-methoxyethyl acrylate, methoxytriethylene glycol methyl acrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and methacrylic acid 8-ethyl-8-tricyclodecyl ester and the like. It is also possible to use glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) meth (meth) acrylate, and (3-ethyl-3-oxetanyl) A cyclic ether group (meth) acrylate compound such as an alkyl) meth (meth) acrylate.

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

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

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

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% to 100 mol%, and 10 mol% to 90 mol% is more preferable. 15 to 85 mol% is preferred.

The content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 mol% to 90 mol% in terms of the so-called liquid crystal alignment, and 15 mol% to 85 Molar% is more preferable, and 20 Molar% to 80 Molar% is more preferable.

The content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 5 mol% to 95 mol% in terms of the so-called liquid crystal alignment, and 10 mol% to 90 mol. Ear% is more preferable, and 15 to 85 mole% is more preferable.

The side chain polymer of the present invention may contain other side chains in addition to the side chain represented by the formula (a), the photoreactive side chain, and the liquid crystal side chain. When the content is less than 100 mol%, the total content of the side chain, the photoreactive side chain, and the liquid crystal side chain represented by the formula (a) is a residual amount.

The method for producing the side chain polymer of this embodiment is not particularly limited, and a general-purpose method that is industrially used can be used. Specifically, it can be manufactured by cationic polymerization, radical polymerization, or anionic polymerization of a vinyl group using a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoints of ease of reaction control and the like.

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent can be used.

A radical thermal polymerization initiator is a compound that generates a radical by heating above a decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), and difluorenyl peroxides (acetamyl peroxide, peroxygen, and the like). Benzamidine oxide, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, Dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutyl cyclohexane peroxide, etc.), alkyl peroxides (nedecanoic acid-tert-butyl peroxide) Esters, tert-butyl peroxide, 2-ethylcyclohexane-tert-pentyl peroxide, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), Azo-based compounds (such as azobisisobutyronitrile and 2,2'-bis (2-hydroxyethyl) azobisisobutyronitrile). Such a radical thermal polymerization initiator may be used singly or in combination of two or more kinds.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that starts radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michelin, 4,4'-bis (diethylamine) benzophenone, xanthone, thioxanthone, Isopropylthioxanthone, 2,4-diethylthioxanthone, 2-ethylanthracene ether, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4 '-Isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-di Methoxy-2-phenylacetophenone, camphor ether, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamine-1- (4-morpholinylphenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 4,4'-bis (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tris (t-butylperoxycarbonyl) benzophenone, 2, 4,6-trimethylbenzylidene diphenylphosphine 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'-pentoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 4- [pN, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -s-triazine, 1,3-bis (tri (Chloromethyl) -5- (2'-chlorobenzene) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzo Azole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- ( o-chlorobenzene) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorobenzene) -4,4', 5,5 ' -(4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorobenzene) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'bis (2,4-dibromobenzene) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis (2,4,6-trichlorobenzene) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylamine Propylpropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinylpropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-Bicyclopentadien-1-yl) -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-peroxyhexylcarbonyl) benzophenone, 3,3'-bis ( (Methoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) benzophenone, 3,4'-bis (methoxycarbonyl) -4,3'-bis (t-butyl Peroxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (t-butylperoxycarbonyl) benzophenone, 2- (3- Methyl-3H-benzo Azole-2-ylidene) -1-naphthalene-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -ylidene) -1- (2- Benzamidine) ethyl ketone and the like. These compounds may be used singly or in combination of two or more kinds.

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 block polymerization method, a solution polymerization method, and the like can be used.

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

Examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl Caprolactam, dimethyl sulfene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, isopropanol, methoxymethylpentanol, dioxene , Ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methylcellulose, ethyl cellosolve, methyl cellosolve B Acid ester, ethyl cellosolve acetate, butylcarbitol, ethylcarbitol, 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, Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, carbonic acid Propylene, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Propyl ester, 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide , 3-ethoxy-N, N-dimethylpropylamine, 3-butoxy-N, N-dimethylpropylamine, and the like.

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

Further, in radical polymerization, oxygen in an organic solvent may cause a polymerization reaction to be hindered. Therefore, it is preferable to use an organic solvent to degas as much as possible.

The polymerization temperature during the 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 system can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a polymer with a high molecular weight. The monomer concentration is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. The reaction is performed at a high concentration in the initial stage, and an organic solvent may be added thereafter.

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

    [Recycling of polymers]    

From the reaction solution of the photosensitive side-chain type polymer capable of exhibiting liquid crystallinity obtained by the above-mentioned reaction, when the generated polymer is recovered, the reaction solution is poured into a poor solvent to precipitate these polymers. Just fine. Examples of poor solvents for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. , Methyl ethyl ether, water, etc. The polymer system which is put into a poor solvent and precipitated can be filtered and recovered, and then dried at normal temperature or heating under normal pressure or reduced pressure. In addition, when the operation of re-dissolving the polymer recovered by precipitation into an organic solvent and repeating the recovery by precipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons. When three or more kinds of poor solvents selected from these are used, the efficiency of purification is further improved, which is preferable.

The molecular weight of the (A) side chain polymer of the present invention is determined by GPC (Gel Permeation Chromatography) method when considering the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film. The weight average molecular weight is preferably from 2000 to 2,000,000, and more preferably from 5,000 to 150,000. Or the aforementioned weight average molecular weight is preferably 2,000 to 1,000,000, and more preferably 5,000 to 200,000.

In the side chain polymer of the component (A) of the present invention, the content of the side chain represented by formula (a) is preferably 5 to 95 mole%, and more preferably 10 to 90 mole%. It is better to use 20 ~ 80 mole%.

    << (B) Organic solvents >>    

The organic solvent used in the polymer composition of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving a 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, dimethyl fluorene, tetramethylurea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, 3-methoxy- N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-bis Methyl-imidazolinone, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, carbonate Propyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether , Diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol Propylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, trimethyl ether Propylene glycol methyl ether and the like. These can be used alone or in combination.

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

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness or the surface smoothness include the following. For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl card Alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropylene Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether , Diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutanone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane , N-octane, diethyl ether, methyl lactate , Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid Butyl propionate, 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-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2- Solvents having low surface tension, such as ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like.

These poor solvents may be used singly or in combination. When using a solvent such as the above, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition, 5 to 80% by mass of the entire solvent is preferable, and 20% by mass is more preferable. 60% by mass.

Examples of the compound that improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polysiloxane-based surfactant, and a nonionic surfactant.

More specific examples include F-Top (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (Made by Sumitomo 3M), AashiGuard (registered trademark) AG710 (made by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMI CHEMICAL), and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and the like shown below.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-Ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazine Heterodecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethyl Oxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane , N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (ethoxyethyl) -3-aminopropyl Trimethoxysilane, N-bis (oxyethyl) -3-amino Propyltriethoxysilane and the like.

Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film to prevent the reduction of electrical characteristics caused by the backlight when constituting a liquid crystal display element, the polymer composition may contain the following phenolic plastics or Additives to epoxy compounds. Although a specific phenolic plastic additive is shown below, it is not limited to this structure.

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and new Pentylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetrakis Glycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamine Methyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, and the like.

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

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin, Carbonyl biscoumarin, aromatic 2-hydroxy ketones, and aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamine) -2- Hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphthothiazole Phthaloline, 2- (β-naphthylmethylene) -3-methylbenzothiazoline, 2- (α-naphthylmethylene) -3-methylbenzothiazoline, 2- (4-Biphenylmethylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylene) -3-methyl-β-naphthothiazoline, 2- (4 -Biphenylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzylmethylene) -3-methyl-β-naphthothiazoline), oxazole Porphyrin (2-benzylidenemethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthylidenemethylene) -3-benzoxazoline, 2- ( α-naphthylmethylene) -3-benzoxazoline, 2- (4-biphenylmethylene) -3-benzoxazoline, 2- (β-naphthylmethylene) (Methyl) -3- Methyl-β-naphthoxazoline, 2- (4-biphenylmethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylmethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroethane naphthalene (5-nitroethanenaphthalene), (2-[(m-hydroxy-p-methoxy) styrene] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, phenethyl Ketals (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopiperan , Azo indole, methyl coumarin and so on.

Aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Acetal.

In addition to the above, in the polymer composition, as long as the effects of the present invention are not impaired, a dielectric material or a conductivity of the liquid crystal alignment film may be changed, and a dielectric material or A conductive substance may be added with a crosslinkable compound for the purpose of increasing the hardness or density of the film when the liquid crystal alignment film is made.

    [Modulation of polymer composition]    

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

In the polymer composition of this embodiment, polymers other than the component (A) may be mixed within a range that does not impair the liquid crystal display ability and the light-sensitive performance. At this time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, and preferably 1% by mass to 50% by mass.

Examples of such other polymers include, for example, poly (meth) acrylates, polyamic acids, polyimines, and the like, which are not photosensitive side-chain polymers that exhibit liquid crystallinity. Polymer, etc.

    <Manufacturing method of substrate with liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>    

The method for manufacturing a substrate with a liquid crystal alignment film of the present invention has the following steps: [I] a photosensitive side chain polymer containing (A) a liquid crystallinity exhibiting liquid crystallinity in a specified temperature range, and (B ) An organic solvent as a special polymer composition, a step of coating 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 [ III] A step of heating the coating film obtained in [II].

Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

In a second aspect of the present invention, the method for manufacturing a substrate having a liquid crystal alignment film of the present invention has the following steps: [I] will contain (A) a photosensitive material exhibiting liquid crystallinity within a specified temperature range; Steps of forming a coating film by applying a side-chain type polymer and (B) an organic solvent as a special polymer composition on a substrate having a conductive film for driving a transverse electric field; [II] coating on [I] A step of irradiating the film with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II].

Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

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

The second substrate is a substrate without a conductive film for lateral electric field driving, instead of a substrate with a conductive film for lateral electric field driving, by using the above steps [I] to [III] (due to the use of a substrate without a lateral electric field) The substrate of the conductive film for driving is sometimes abbreviated as steps [I '] to [III'] for the sake of convenience in this application, so that a second substrate having a liquid crystal alignment film provided with an alignment control capability can be obtained.

A method for manufacturing a lateral electric field-driven liquid crystal display device has the following steps: [IV] The first and second substrates obtained above are interposed with a liquid crystal, and the liquid crystal alignment films of the first and second substrates face each other. Steps of opposing arrangement to obtain a liquid crystal display element. According to this, a lateral electric field drive type liquid crystal display element can be obtained.

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

    <Step [I]>    

In step [I], a substrate containing a conductive film for driving a lateral electric field is coated with a polymer composition containing a photosensitive side chain polymer exhibiting liquid crystallinity in a predetermined temperature range and an organic solvent. Form a coating film.

    <Substrate>    

The substrate is not particularly limited, and if the manufactured liquid crystal display element is a transmissive type, it is preferable to use a substrate having high transparency. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate, or a polycarbonate substrate can be used.

In addition, considering application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

    <Conductive film for lateral electric field drive>    

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

As the conductive film, if the liquid crystal display element is of a transmissive type, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like are mentioned, but it is not limited to these.

In the case of a reflective liquid crystal display element, a material that reflects light, such as aluminum, may be used as the conductive film, but it is not limited thereto.

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

The method for applying the polymer composition described above to a substrate having a conductive film for lateral electric field driving is not particularly limited.

The coating method is generally carried out in the industry by screen printing, lithography, flexographic printing, or inkjet. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spinner method (spin coating method), or a spray method, and these can be used depending on the purpose.

After coating the polymer composition on a substrate having a conductive film for lateral electric field drive, the heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven is used at 50 to 200 ° C, preferably 50 to 200 ° C. A coating film 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, the power consumption of the liquid crystal display element is disadvantageous. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 nm to 300 nm, and more preferably 10nm ~ 150nm.

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

    <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 through a polarizing plate through a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength ranging from 100 nm to 400 nm can be used. It is preferable to select the most suitable wavelength depending on the type of coating film to be used, an intervening filter, and the like. In addition, for example, an ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected so as to selectively induce a photo-crosslinking reaction. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

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

    <Step [III]>    

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

As the heating system, heating means such as a hot plate, a thermal cycle 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 coating film used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range in which a side chain polymer exhibits liquid crystallinity (hereinafter referred to as a liquid crystallinity exhibiting temperature). When a film surface such as a coating film is used, the liquid crystal display temperature at the surface of the coating film can be predicted to be lower than the liquid crystal display temperature at the time of a photosensitive side-chain polymer that exhibits liquid crystal properties as a whole. Therefore, the heating temperature is preferably within a temperature range in which the liquid crystal display temperature of the coating film surface is exhibited. That is, the temperature range of the heating temperature after the irradiation with polarized ultraviolet light is set to a lower limit of a temperature lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain polymer used by the lower limit, and the temperature range is lower than the liquid crystal temperature range It is preferable that the temperature in which the upper limit is 10 ° C lower is the temperature in the range of the upper limit. If the heating temperature is lower than the above temperature range, the effect of increasing the anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is higher than the above temperature range, the state of the coating film is close to Due to the tendency of an isotropic liquid state (isotropic phase), it is sometimes difficult to reorient in one direction by self-organization.

However, the liquid crystal display temperature is higher than the glass transition temperature (Tg) of the side chain polymer or the surface of the coating film from the solid phase to the liquid crystal phase, and the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase). Temperature below the homogeneous phase transfer temperature (Tiso).

By having the above steps, in the manufacturing method of the present invention, anisotropy can be efficiently introduced into the coating film. In addition, a substrate with a liquid crystal alignment film can be manufactured efficiently.

    <Step [IV]>    

[IV] Step is the same as that obtained in the above [I '] to [III'] on the substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving obtained in [III]. A substrate (second substrate) with a liquid crystal alignment film having a conductive film is disposed opposite to each other through the liquid crystal alignment films, and a liquid crystal cell is produced by a known method to produce a lateral electric field. Steps of driving a liquid crystal display element. Steps [I '] to [III'] can be performed in the same manner as in step [I] except that the substrate having the conductive film for lateral electric field driving is used instead of the substrate having the conductive film for lateral electric field driving. I] to [III] are performed in the same manner. The difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the above-mentioned conductive film, so the description of steps [I '] to [III'] is omitted.

If an example of the production of a liquid crystal cell or a liquid crystal display device can be cited, the following examples can be prepared: preparing the above-mentioned first and second substrates, dispersing a spacer on the liquid crystal alignment film of one substrate, and making the liquid crystal alignment film surface inside A method of bonding another substrate and injecting liquid crystal under reduced pressure and sealing, or a method of bonding the substrate and sealing after dropping liquid crystal on the liquid crystal alignment film surface where the spacers are dispersed. In this case, it is preferable that the substrate on one side is a substrate using an electrode having a comb-like structure for driving a lateral electric field. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer will determine the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for manufacturing a substrate with a coating film according to the present invention, a polymer composition is coated on the substrate to form a coating film, and then polarized ultraviolet rays are irradiated. Next, by applying heating to efficiently introduce anisotropy into the side-chain polymer film, a substrate with a liquid crystal alignment film having an alignment control capability for liquid crystals is manufactured.

The coating film used in the present invention utilizes the principle of photoreaction of side chains and molecular realignment induced by self-organization based on liquid crystallinity to achieve an efficient introduction of anisotropy into the coating film. In the manufacturing method of the present invention, when the side chain polymer has a structure having a photo-crosslinkable group as a photoreactive group, the side chain polymer is used to form a coating film on a substrate, and then the polarized ultraviolet light is irradiated. Next, After heating, a liquid crystal display element is manufactured.

Therefore, the coating film used in the method of the present invention sequentially irradiates the coating film with polarized ultraviolet rays and heat treatment, so that anisotropy can be efficiently introduced, and a liquid crystal alignment film having excellent alignment control ability can be produced.

In addition, in the coating film used in the method of the present invention, the irradiation amount of the coating film with polarized ultraviolet rays and the heating temperature in the heat treatment are optimized. This makes it possible to efficiently introduce anisotropy into the coating film.

The amount of polarized ultraviolet radiation that is most suitable for efficiently introducing anisotropy into the coating film used in the present invention corresponds to the photocrosslinking reaction or photoisomerization of the photosensitive groups in the coating film. The amount of the chemical reaction or the photo-Frys rearrangement reaction reaches the most suitable amount of polarized ultraviolet radiation. As a result of irradiating the coating film used in the present invention with polarized ultraviolet light, if there are few photosensitive groups in the side chain that cause a photocrosslinking reaction, a photoisomerization reaction, or a photo-Fries rearrangement reaction, it will not be sufficient The amount of light reaction. In this case, even if heating is performed later, sufficient self-organization is not performed. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to a structure having a photo-crosslinkable group, if the number of photosensitive groups of the side chain undergoing the crosslinking reaction is excessive, the distance between the side chains is large. The crosslinking reaction will proceed excessively. At this time, the obtained film may become rigid, which may hinder the progress of self-organization by heating. In addition, as for the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to a structure having a photo-Fries rearrangement group, if the photosensitive group of the side chain undergoing the photo-Fries rearrangement reaction is excessive, The liquid crystallinity of the coating film will be too low. In this case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-organization by heating afterwards. Furthermore, when polarized ultraviolet rays are irradiated to a structure having a light Fryce rearrangement group, if the amount of ultraviolet rays is excessive, the side chain polymer will undergo photodecomposition, which hinders self-organization caused by heating afterwards. How it works.

Therefore, in the coating film used in the present invention, the most suitable amount of the photo-crosslinking reaction, the photo-isomerization reaction, or the photo-Frys rearrangement reaction of the photosensitive group of the side chain by irradiation of polarized ultraviolet rays. It is more preferable that it is 0.1 mol% to 40 mol% as the photosensitive group of the side chain polymer film, and it is more preferable that it is 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the side chain that undergoes the photoreaction to such a range, self-organization during subsequent heat treatment can be efficiently performed, and anisotropy can be efficiently formed in the film.

In the coating film used in the method of the present invention, the photocrosslinking reaction or photoisomerization of the photosensitive group in the side chain of the side chain polymer film can be optimized by optimizing the irradiation amount of polarized ultraviolet rays. The amount of the reaction, or photo-Fries rearrangement reaction, is optimized. In addition, it is possible to efficiently introduce anisotropy into the coating film used in the present invention together with the subsequent heat treatment. In this case, the appropriate amount of polarized ultraviolet rays can be evaluated based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, the ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet light after the irradiation of the polarized ultraviolet light and the ultraviolet absorption in a direction perpendicular to the polarization direction of the polarized ultraviolet light were measured. △ A was evaluated from the measurement results of ultraviolet absorption. The aforementioned ΔA is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of polarized ultraviolet rays in the coating film and the ultraviolet absorbance in a direction perpendicular to the polarization direction of polarized ultraviolet rays. . In addition, the maximum value (ΔAmax) of ΔA achieved in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays realizing the same were obtained. In the manufacturing method of the present invention, a preferable amount of polarized ultraviolet ray irradiated in the manufacture of the liquid crystal alignment film can be determined based on the amount of polarized ultraviolet ray irradiation to achieve the ΔAmax.

In the manufacturing method of the present invention, it is preferable that the irradiation amount of the polarized ultraviolet ray irradiated to the coating film used in the present invention is within a range of 1% to 70% of the amount of the polarized ultraviolet ray that achieves ΔAmax. It is more preferable to be in the range of 1% to 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 of ΔAmax is equivalent to the sensitivity of the side chain polymer film. 0.1 to 20 mol% of the total amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

Based on the above, in the manufacturing method of the present invention, in order to efficiently introduce anisotropy into the coating film, the liquid crystal temperature range of the side chain polymer can be used as a reference to determine the appropriate heating temperature as described above. . 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., the heating temperature after polarized ultraviolet radiation is preferably set to 90 ° C. to 190 ° C. With such settings, the coating film used in the present invention can impart greater anisotropy.

With such settings, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light or heat.

In the above manner, the substrate for a lateral electric field drive type liquid crystal display element manufactured by the method of the present invention or a lateral electric field drive type liquid crystal display element having the substrate has excellent reliability and can be suitably used for large screens and has a high Fine LCD TV and more.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

    [Example]    

Examples are given below to explain the present invention in more detail, but the present invention is not limited to these.

The structure of the (meth) acrylate compound used in an Example is shown below.

    <Polymerizable compound>    

MA-1 was synthesized according to a synthesis method described in a patent document (WO2011-084546).

MA-2 is synthesized according to a synthesis method described in a patent document (Japanese Patent Application Laid-Open No. 9-118717).

MA-3 is synthesized according to the same synthesis method as MA-2.

MA-4 to MA-8 are novel compounds not disclosed in the literature and the like, so the synthetic method is described in detail below.

MA-9 is synthesized in accordance with a synthesis method described in a patent document (Japanese Patent Application Laid-Open No. 2006-308878).

The products described in the following Synthesis Examples 1 to 5 were identified by ¹ H-NMR analysis (the analysis conditions are as follows).

Device: Varian NMR System 400 NB (400MHz)

Measurement solvents: CDCl ₃ , DMSO-d ₆

Reference substance: Tetramethylsilane (TMS) (δ0.0ppm for ¹ H)

    <Synthesis of Synthesis Example 1 MA-4>    

    <Synthesis of MA-4A>    

Tetrahydrofuran (393.5 g) was charged with ethyl 4-bromobenzoate (78.7 g, 344 mmol) and diethylamine (125.8 g), 5-hexyn-1-ol (43.8 g), and copper iodide ( 2.6 g), and after setting it under a nitrogen atmosphere, bis (triphenylphosphine) palladium (II) dichloride (4.8 g) was added and allowed to react at 60 ° C. for 7 hours. After completion of the reaction, 3.9 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added, and after stirring at room temperature for 1 hour, the activated carbon was removed by filtration. Next, tetrahydrofuran was removed by concentration under reduced pressure, diluted with ethyl acetate, and then washed three times with pure water. To the obtained organic phase, 3.9 g of activated carbon (commercial name: special dried egret, manufactured by Enviro Chemicals, Japan) was added, and the mixture was stirred at room temperature for 1 hour, and filtered and concentrated under reduced pressure to obtain 103 g of MA-4A. (Crude yield: 122%, property: brown oily compound).

    <Synthesis of MA-4B>    

The obtained MA-4A (50.4 g) was dissolved in methanol (151.2 g) and pure water (100.8 g), and potassium hydroxide (17.2 g) was added and 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 make the aqueous phase side acidic, and then the aqueous hydrochloric acid phase was removed. Next, after washing the organic phase twice with pure water, 2.5 g of activated carbon (trade name: special dry egret, manufactured by Enviro Chemicals, Japan) was added to the organic phase, and the mixture was stirred at room temperature for 1 hour. The activated carbon was removed by filtration and concentrated under reduced pressure to obtain pale brown crystals. Isopropyl alcohol was added to the obtained crystals and the solution became a uniform solution by setting the temperature to 60 ° C. Then, acetonitrile, which was a poor solvent, was added to perform recrystallization, and then filtered and dried to obtain 25.5 g of MA-4B (2 Stage yield: 70%, Properties: light gray crystals).

    <Synthesis of MA-4>    

Tetrahydrofuran (146.4 g) was charged with the obtained MA-4B (24.4 g, 112 mmol) and triethylamine (28.5 g), and methacrylic acid chloride was added dropwise under ice cooling in a nitrogen environment. (25.9g). After completion of the dropping, the reaction was allowed to proceed for 17 hours at room temperature. After the reaction was completed, the reaction solution was diluted with ethyl acetate, washed three times with pure water, and the organic phase was concentrated under reduced pressure to obtain a yellow oily compound. Next, 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, and then the aqueous hydrochloric acid phase was removed, followed by washing with pure water three times. To the recovered organic phase was added 1.3 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan), and the mixture was stirred at room temperature for 1 hour, and then filtered and concentrated under reduced pressure to obtain a brown oily compound. . Next, acetonitrile was added and heated to 50 ° C. to obtain a homogeneous solution. The crystals were precipitated by ice cooling, and then filtered to obtain a crude product. Next, the obtained crude product was slurry-washed with a mixed solution of acetonitrile and tetrahydrofuran, and filtered and dried to obtain 12.4 g of MA-4 (yield: 39%, properties: white crystals).

¹ H-NMR (400MHz) in DMSO-d ₆ : 1.61-1.63 ppm (m, 2H), 1.64-1.78 ppm (m, 2H), 1.89 ppm (s, 3H), 2.51-2.54 ppm (m, 2H) , 4.16ppm (t, 2H), 5.67-5.69ppm (m, 1H), 6.04-6.05ppm (m, 1H), 7.48-7.51ppm (m, 2H), 7.88-7.91ppm (m, 2H), 13.1 ppm (s, 1H).

    <Synthesis of Synthesis Example 2 MA-5>    

    <Synthesis of MA-5A>    

Tetrahydrofuran (343.5 g) was charged with ethyl 4-bromobenzoate (68.7 g, 300 mmol) and diethylamine (109.7 g), 6-heptyn-1-ol (43.7 g), and copper iodide ( 2.3 g). After setting it under a nitrogen atmosphere, bis (triphenylphosphine) palladium (II) dichloride (4.2 g) was added and allowed to react at 60 ° C for 23 hours. After the reaction was completed, 6.8 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added and stirred at room temperature for 1 hour, and then the activated carbon was removed by filtration. Next, tetrahydrofuran was removed by concentration under reduced pressure, diluted with ethyl acetate, and then washed three times with pure water. To the obtained organic phase, 6.8 g of activated carbon (commercial name: special dried egret, manufactured by Enviro Chemicals, Japan) was added, and the mixture was stirred at room temperature for 1 hour, and filtered and concentrated under reduced pressure to obtain MA-5A 98.3. g (crude yield: 126%, properties: brown oily compound).

    <Synthesis of MA-5B>    

The obtained MA-5A (49.3 g) was dissolved in methanol (98.6 g) and pure water (98.6 g), and potassium hydroxide (15.0 g) was added and 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 make the aqueous phase side acidic, and then the aqueous hydrochloric acid phase was removed. Next, after washing the organic phase twice with pure water, 4.9 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added to the organic phase, and the mixture was stirred at room temperature for 1 hour. The activated carbon was removed by filtration and concentrated under reduced pressure to obtain pale brown crystals. Isopropanol was added to the obtained crystals and the solution became a uniform solution by setting the temperature to 60 ° C. Then, acetonitrile, which was a poor solvent, was added and then recrystallized. After filtering and drying, MA-5B 25.1 g (2 Stage yield: 72%, Properties: pale yellow crystals).

    <Synthesis of MA-5>    

Tetrahydrofuran (125.2g) was charged with the obtained MA-5B (25.1g, 108mmol) and triethylamine (30.4g), and methacrylic acid chloride was added dropwise under ice cooling in a nitrogen environment. (24.9g). After completion of the dropping, the reaction was allowed to proceed for 4 hours at room temperature. After completion of the reaction, the reaction solution was diluted with ethyl acetate, washed three times with pure water, and the organic phase was concentrated under reduced pressure to obtain a yellow oily compound. Next, the oily compound was diluted with acetonitrile (76.0 g) and a 1.0 M aqueous hydrochloric acid solution (50.0 g), and allowed to react at 50 ° C for 2 days. After completion of the reaction, the reaction solution was diluted with ethyl acetate, and then the aqueous hydrochloric acid phase was removed, followed by washing with pure water three times. To the recovered organic phase was added 1.3 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan), and the mixture was stirred at room temperature for 1 hour, and then filtered and concentrated under reduced pressure to obtain a brown oily compound. . Next, acetonitrile was added and heated to 50 ° C. to obtain a homogeneous solution. The crystals were precipitated by ice cooling, and then filtered to obtain a crude product. The crude product obtained was recrystallized from a mixed solution of acetonitrile and tetrahydrofuran, and filtered and dried to obtain MA-5 12.6 g (yield: 39%, properties: white crystals).

¹ H-NMR (400MHz) in DMSO-d ₆ : 1.44-1.71 ppm (m, 6H), 1.87 ppm (s, 3H), 2.46-2.52 ppm (m, 2H), 4.12 ppm (t, 2H), 5.65 -5.66ppm (m, 1H), 6.01-6.02ppm (m, 1H), 7.46-7.50ppm (m, 2H), 7.89-7.91ppm (m, 2H), 13.1ppm (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 make the aqueous phase side acidic, and then the aqueous hydrochloric acid phase was removed. Next, after washing the organic phase three times with pure water, 4.7 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added to the organic phase, and the mixture was stirred at room temperature for 1 hour. The activated carbon was removed by filtration and concentrated under reduced pressure to obtain a crude product. Next, the obtained crude product was dissolved by heating at 60 ° C in ethyl acetate, and crystals were precipitated by cooling with ice, and 24.9 g of MA-4B was obtained by filtering and drying.

    <Synthesis of MA-6A>    

Tetrahydrofuran (124.5 g) was charged with the obtained MA-4B (24.9 g) and a 5% palladium carbon powder (aqueous product) of the STD type (trade name: nechemcat, 2.5 g). The reaction was carried out under a hydrogen pressure of MPa for 17 hours. After the reaction was completed, filtration was performed and the slurry was washed with acetonitrile to obtain 20.7 g of MA-6A (3 stage yield: 53%, properties: pale yellow crystals).

    <Synthesis of MA-6>    

Tetrahydrofuran (124.2g) was charged with MA-6A (20.7g), triethylamine (23.6g), and N, N-dimethyl-4-aminopyridine (0.53g). Methacrylic acid chloride (22.4 g) was added dropwise under ice-cooling, and the mixture was allowed to react at room temperature for 2 hours. After completion of the reaction, the reaction 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 obtain a yellow oily compound. Next, 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 aqueous hydrochloric acid phase was diluted and removed with ethyl acetate, and then the organic phase was washed three times with pure water. To the recovered organic phase was added 1.0 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan), and the mixture was stirred at room temperature for 1 hour, and then filtered and concentrated under reduced pressure to obtain a brown oily compound. . Next, acetonitrile was added and heated at 50 ° C. to obtain a homogeneous solution. The crystals were precipitated by ice-cooling and filtered to obtain a crude product. By recrystallizing the crude product with acetonitrile and tetrahydrofuran, 10.1 g of MA-6 was obtained (yield: 37%, properties: white crystals).

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), 2.64 ppm (t, 2H), 4.07 ppm (t, 2H), 5.65-5.67 ppm (m, 1H), 6.00-6.01 ppm (m, 1H), 7.30-7.32 ppm (m, 2H), 7.84-7.86 ppm (m, 2H), 12.8 ppm ( s, 1H)

    <Synthesis of Synthesis Example 4 MA-7>    

    <Synthesis of MA-7A>    

MA-5A (49.0 g) was dissolved in methanol (98.8 g) and pure water (100.6 g), and potassium hydroxide (14.8 g) was added and 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 make the aqueous phase side acidic, and then the aqueous hydrochloric acid phase was removed. Next, after washing the organic phase three times with pure water, 4.9 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added to the organic phase, and the mixture was stirred at room temperature for 1 hour. The activated carbon was removed by filtration, and concentrated under reduced pressure to obtain a crude MA-5B product. Next, the obtained crude product was dissolved in tetrahydrofuran (119.1 g), and 5% palladium carbon powder (aqueous product) was filled with an STD type (trade name: nechemcat company, 4.7 g). It was allowed to react under pressure for 19 hours. After the completion of the reaction, filtration was performed and the slurry was washed with acetonitrile to obtain 27.7 g of MA-7A (3 stage yield: 78%, properties: pale yellow crystals).

    <Synthesis of MA-7>    

Tetrahydrofuran (166.7g) was charged with MA-7A (26.1g), triethylamine (30.3g), and N, N-dimethyl-4-aminopyridine (0.71g). Methacrylic acid chloride (28.3 g) was added dropwise under ice-cooling, and the reaction was performed at room temperature for 2 hours. After completion of the reaction, it was diluted with ethyl acetate, washed once with a 1.0 M hydrochloric acid aqueous solution, once with pure water, and the organic phase was concentrated under reduced pressure to obtain a yellow oily compound. Next, 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 aqueous hydrochloric acid phase was diluted and removed with ethyl acetate, and then the organic phase was washed three times with pure water. To the recovered organic phase was added 1.3 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan), and the mixture was stirred at room temperature for 1 hour, and then filtered and concentrated under reduced pressure to obtain a brown oily compound. . Next, acetonitrile was added and heated at 50 ° C. to obtain a homogeneous solution. The crystals were precipitated by ice-cooling and filtered to obtain a crude product. 5.3 g of MA-7 was obtained by recrystallizing the crude product using acetonitrile and tetrahydrofuran (yield: 16%, properties: white crystals).

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), 2.63 ppm (t, 2H), 4.08 ppm (t, 2H), 5.65-5.67ppm (m, 1H), 6.00-6.01ppm (m, 1H), 7.30-7.32ppm (m, 2H), 7.84-7.87ppm (m, 2H), 12.8ppm ( s, 1H)

    <Synthesis Example 5 Synthesis of MA-8>    

    <Synthesis of MA-8A>    

In dichloromethane (802.0 g), propargyl alcohol (200.5 g) and p-pyridinium tosylate (44.9 g) were charged, and 3,4-di Hydrogen-2H-pyran (361.7 g). After the dropwise addition, the reaction temperature was set to room temperature and allowed to react for 5 hours. After the reaction, the organic phase was washed three times with pure water and subjected to magnesium sulfate dehydration treatment, and then concentrated under reduced pressure to obtain 522 g of a crude MA-8A product (crude yield: 104%, properties: pale yellow Oily compound).

    <Synthesis of MA-8B>    

Toluene (500.0 g) was charged with 1-bromo-4-iodobenzene (100.0 g) and piperidine (60.1 g), copper iodide (4.04 g), and bis (triphenylphosphine) palladium (II) diamine. Chloride (7.44 g) was stirred under a nitrogen atmosphere for 2 minutes. Next, MA-8A (69.4 g) was added dropwise over 30 minutes. During the dropwise addition, the reaction temperature rapidly increased. Therefore, the dropwise operation was performed at a temperature of about 23 ° C. by cooling with water. After the completion of the dropping, toluene (500.0 g) was added and reacted for 1 hour because of poor stirring. 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, and then the organic phase was recovered. Next, 10.0 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added to the recovered organic phase, and the mixture was stirred for 1 hour. After filtering and concentration under reduced pressure, 118.2 g of a crude MA-8B product was obtained (Crude yield: 113%, properties: brown oily compound).

    <Synthesis of MA-8C>    

N, N-dimethylformamide (300.5 g) and pure water (120.2 g) were charged with 4-hydroxyphenylboronic acid Ester (60.1g), MA-8B (92.6g), cesium carbonate (179.8g), by adding tri-ter-butylphosphine (3.70g) and bis (triphenylphosphine) palladium (II) under a nitrogen environment ) Dichloride (5.75 g) and allowed to react at 60 ° C for 7 hours. After completion of the reaction, it was diluted with ethyl acetate, washed once with 1.0 M aqueous hydrochloric acid solution, and washed three times with pure water. To the recovered organic phase, 6.0 g of activated carbon (commercial name: special dried egret, manufactured by Enviro Chemicals, Japan) was added and stirred for 1 hour, and the crude product was obtained by filtration and concentration under reduced pressure. By purifying the obtained crude product through a silica gel column (hexane: ethyl acetate = 6: 1 volume ratio), MA-8C 60.2 g (yield: 72%, property: light orange) was obtained. crystallization).

    <Synthesis of MA-8D>    

Tetrahydrofuran (120.3g) was charged with MA-8C (42.0g) and 5% palladium carbon powder (aqueous product) STD type (trade name: nechemcat company, 3.36g), and under a hydrogen pressure of 0.4MPa The reaction was allowed to proceed for 28 hours. After completion of the reaction, filtration and concentration under reduced pressure were performed. The crude product obtained was subjected to silica gel column purification (hexane: ethyl acetate = 6: 1 volume ratio) to obtain 29.0 g of MA-8D (yield: 68%, property: pale yellow oil). Like compound).

    <Synthesis of MA-8E>    

Tetrahydrofuran (124.8g) was charged with MA-8D (25.0g), 4-methoxycinnamic acid (15.0g), N, N-dimethyl-4-aminopyridine (1.00g), and 1-ethyl The methyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (18.4 g) was reacted at room temperature under a nitrogen environment for 18 hours. After the reaction is completed, the reaction solution is poured into pure water to obtain a crude product of the reactant. By washing the obtained crude product with a slurry using 2-propanol, 34.8 g of MA-8E was obtained (yield: 92%, properties: white crystals).

    <Synthesis of MA-8F>    

In ethanol (278.0 g), MA-8E (34.8 g) and pyridinium p-toluenesulfonate (3.70 g) were charged and reacted at 70 ° C for 21 hours. After the reaction is completed, the reaction solution is poured into pure water to obtain a crude product of the reactant. Next, the obtained crude product was slurry-washed with methanol, and recrystallized with tetrahydrofuran and methanol to obtain 25.7 g of MA-8F (yield: 90%, properties: white crystals).

    <Synthesis of MA-8>    

Tetrahydrofuran (278.4 g) was charged with MA-8F (25.1 g) and triethylamine (8.52 g), and methacrylic acid chloride (8.30 g) was added dropwise under ice-cooling in a nitrogen environment. After the dropwise addition was completed, the reaction temperature was set to room temperature and the reaction was allowed to proceed for 20 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate at 45 ° C, washed three times with pure water, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was re-dissolved in tetrahydrofuran, 2.5 g of activated carbon (trade name: special dried egret, manufactured by Enviro Chemicals, Japan) was added, and the mixture was stirred at room temperature for 1 hour and then filtered. Next, the obtained solution was concentrated under reduced pressure, and after setting the total internal weight to 151.4 g, methanol was added to precipitate crystals. The obtained crystals were slurry-washed with ethyl acetate, and filtered and dried to obtain 15.2 g of MA-8 (yield: 51%, properties: pale yellow crystals).

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), 5.56ppm (s, 1H), 6.11ppm (s, 1H), 6.52ppm (d, 1H), 6.92-6.96ppm (m, 2H), 7.21-7, 27ppm (m, 4H), 7.49- 7.61ppm (m, 6H), 7.85ppm (d, 1H).

The abbreviations of the organic solvents used in Examples and the like are as follows.

NMP: N-methyl-2-pyrrolidone

BC: ethylene glycol monobutyl ether

THF: tetrahydrofuran

PGME: 1-methoxy-2-propanol

    <Determination of Molecular Weight of Polymer>    

In the examples, the molecular weight of the (meth) acrylic polymer is a normal temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex, and a column (KD-803, KD-805) manufactured by Shodex. ), And the measurement was performed in the following manner.

Column temperature: 50 ℃

Eluent: DMF (lithium bromide-hydrate (LiBr‧H ₂ O) as additive is 30mmol / L, phosphoric acid‧anhydrous crystal (o-phosphoric acid) is 30mmol / L, THF is 10mL / L)

Flow rate: 1.0mL / min

Standard samples for the production of calibration lines: TSK standard polyethylene oxide (molecular weight of approximately 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight of approximately 12,000, 4,000, 1,000) produced by Polymer Laboratories.

    <Polymerization example 1>    

MA-1 (13.3g, 40.0mmol) and MA-2 (18.4g, 60.0mmol) were dissolved in THF (182.3g), and after degassing with a diaphragm pump, 2,2'-azobisisobutyl Nitrile (0.82 g, 5.0 mmol) was degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dropped into diethyl ether (1500 ml), and the obtained 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>    

After 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) and degassed by a diaphragm pump, 2,2'-Azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 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. This polymer had a number average molecular weight of 54,000 and a weight average molecular weight of 100,000.

    <Polymerization Example 3>    

After dissolving 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) in THF (11.5 g) and degassing with a diaphragm pump, 2,2'-Azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 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 a methacrylate polymer powder. This polymer had a number average molecular weight of 50,000 and a weight average molecular weight of 100,000.

    <Polymerization Example 4>    

After dissolving 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) in THF (11.4 g) and degassing with a diaphragm pump, 2,2'-Azobisisobutyronitrile (0.044 g, 0.27 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 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. This polymer had a number average molecular weight of 49,000 and a weight average molecular weight of 100,000.

    <Polymerization example 5>    

After dissolving 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) in THF (7.7 g) and degassing with a diaphragm pump, 2,2'-Azobisisobutyronitrile (0.030 g, 0.18 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 96 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. This 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. This polymer had a number average molecular weight of 38,000 and a weight average molecular weight of 90,000.

    <Polymerization Example 6>    

MA-3 (2.0 g, 6.9 mmol) was dissolved in THF (11.7 g), and after degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.035 g, 0.21 mmol) was added, and again Degas. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 103 g of methanol: pure water (1: 1), and the obtained precipitate was filtered. This 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. This polymer had a number average molecular weight of 35,000 and a weight average molecular weight of 65,000.

    <Polymerization example 7>    

MA-4 (1.0 g, 3.5 mmol) was dissolved in THF (4.1 g), and after degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.017 g, 0.10 mmol) was added, and again Degas. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 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 of methacrylate polymer powder (P7). This polymer had a number average molecular weight of 35,000 and a weight average molecular weight of 68,000.

    <Polymerization example 8>    

MA-6 (0.99 g, 3.4 mmol) was dissolved in THF (4.0 g), and after degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.017 g, 0.10 mmol) was added, and again Degas. Then, it was made to react at 60 degreeC for 13 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into 50 g of acetonitrile, and the obtained precipitate was filtered. This 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 number average molecular weight of this polymer was 38,000, and the weight average molecular weight was 74,000.

    <Polymerization Example 9>    

MA-8 (2.05 g, 4.5 mmol) was dissolved in THF (18.7 g), and after degassing with a diaphragm pump, 2,2'-azobisisobutyronitrile (0.022 g, 0.13 mmol) was added, and again Degas. Then, it was made to react at 60 degreeC for 14 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dropped into 208 g of methanol, and the obtained precipitate was filtered. This 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 33,000, and the weight average molecular weight was 48,000.

    <Polymerization Example 10>    

The methacrylate polymer (P10) of MA-9 was synthesized according to the synthesis method described in Patent Literature (Japanese Patent Application 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 it was dissolved by stirring at room temperature for 12 hours. BC (7.0 g) was added to this solution to confirm polymer solubility.

    <Examples 2 to 4, Comparative Example 1>    

The polymer solubility of Examples 2 to 4 was confirmed by the same method as in Example 1. In addition, Comparative Example 1 also confirmed the polymer solubility 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 polymer was dissolved by stirring 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 polymer was dissolved by stirring 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 polymer was dissolved by stirring at room temperature for 12 hours to confirm polymer solubility.

The solubility test results of Examples 5, 6, and Comparative Example 2 are shown in Table 2.

    <Solubility test>         <Example 7>    

NMP (0.96 g) was added to 0.05 g of the obtained methacrylate polymer powder (P9), and it 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 it 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 following results were confirmed. Compared with the conventional polymerization of the ether-bondable polymerizable compounds (MA-1 to MA-3, MA-9), A polymer obtained by copolymerization. The polymer obtained by homopolymerizing and copolymerizing a polymerizable compound (MA-4 to MA-8) using a single bond or a triple bond as a linking group in the present invention dissolves BC or PGME. Sex is for promotion. Therefore, it is taught that a polymer obtained by homopolymerization or copolymerization of an acrylic monomer having a single bond or a triple bond as a linking group can expand solvent selectivity by using the polymer.

    <Production of liquid crystal alignment agent>         <Example 8>    

NMP (7.6 g) was added to 0.4 g of the obtained methacrylate polymer powder (P2), and it was stirred at room temperature for 3 hours to dissolve it. BC (2.0 g) was added to the solution, and a liquid crystal alignment agent (A-1) was obtained by stirring.

    <Example 9>    

NMP (7.6 g) was added to 0.4 g of the obtained methacrylate polymer powder (P3), and it was stirred at room temperature for 3 hours to dissolve it. BC (2.0 g) was added to the solution, and a liquid crystal alignment agent (A-2) was obtained by stirring.

    <Example 10>    

NMP (7.6 g) was added to 0.4 g of the obtained methacrylate polymer powder (P4), and it was stirred at room temperature for 3 hours to dissolve it. BC (2.0 g) was added to the solution, and a liquid crystal alignment agent (A-3) was obtained by stirring.

    <Example 11>    

NMP (7.6 g) was added to 0.4 g of the obtained methacrylate polymer powder (P5), and it was stirred at room temperature for 3 hours to dissolve it. BC (2.0 g) was added to the solution, and a liquid crystal alignment agent (A-4) was obtained by stirring.

    <Example 12>    

Trichloromethane (9.8 g) was added to 0.2 g of the obtained methacrylate polymer powder (P9), and it was dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal alignment agent (A-5). .

    <Fabrication of Ordered Parameter Measurement Board>         <Example 13>    

Using the liquid crystal alignment agent (A-1) obtained in Example 8, a substrate for order parameter measurement was produced according to the procedure shown below. The substrate was a quartz substrate having a size of 40 mm × 40 mm and a thickness of 1.0 mm.

The liquid crystal alignment agent (A-1) obtained in Example 8 was filtered using a 1.0 μm filter, and then spin-coated on a quartz substrate and dried on a 70 ° C. hot plate for 90 seconds to form a 100 nm film. Liquid crystal alignment film. Next, the coating film surface was irradiated with ultraviolet light of 313 nm and 5 to 50 mJ / cm ² through 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>    

Regarding the liquid crystal alignment agents (A-2 to A-4) obtained in Examples 9 to 11, the same method as that of A-1 was also used to produce an order parameter measurement substrate.

    <Example 17>    

Using the liquid crystal alignment agent (A-5) obtained in Example 12, a substrate for order parameter measurement was produced according to the procedure shown below. The substrate was a quartz substrate having a size of 40 mm × 40 mm and a thickness of 1.0 mm.

The liquid crystal alignment agent (A-5) obtained in Example 12 was filtered with a 1.0 μm filter, and then spin-coated onto a quartz substrate, and dried on a 70 ° C. hot plate for 90 seconds to form a 200 nm film. Liquid crystal alignment film. Next, the coating film surface was irradiated with ultraviolet light of 313 nm at 50 to 1000 mJ / cm ² through 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>    

In order to measure the optical anisotropy of the liquid crystal alignment film using the substrate with the liquid crystal alignment film produced as described above, S is calculated as an order parameter from the absorbance of polarized light by the following formula.

Here, A _para represents the absorbance in a parallel direction with respect to the polarized UV direction of the irradiation, and A _per represents the absorbance in the vertical direction with respect to the polarized UV direction of the irradiation. A _large refers to the absorbance with a larger value when comparing the absorbance in the parallel and vertical directions; A _small refers to the absorbance with a smaller value when comparing the absorbance in the parallel and vertical directions. The closer the absolute value [S] of the in-plane alignment degree to 1, the more uniform the alignment state is. The closer the ordered parameter is to 1 or -1, the more consistent the alignment state is.

Tables 4 and 5 show the absolute values [S] of the calculated order parameters. Still, the absolute values of the ordered parameters are expressed according to the following criteria.

○: 0.5 or more

○ △: 0.4 or more to less than 0.5

△: 0.3 or more to less than 0.4

×: less than 0.3

The absorbance was measured using a UV-visible near-infrared spectrophotometer U-3100PC manufactured by Shimadzu Corporation.

As shown in Tables 4 and 5, the following results were confirmed. The polymers P2 to P5 obtained by copolymerizing the polymerizable compound (MA4 to MA7) using a single bond or a triple bond as a linking group according to the present invention. The values of the ordering parameters of the liquid crystal alignment agents A1 to A4 including the polymers P2 to P5 and the liquid crystal alignment agent A5 including the polymers P9 are expressed as about 0.5 to 0.4, and can function as liquid crystal alignment films.

Claims (10)

A polymer composition characterized in that (A) a polymer composition containing (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specified temperature range, and (B) an organic solvent, The component resin contains a side chain represented by the following formula (a). (In the formula (a), L is a linear or branched alkylene group having 1 to 16 carbon atoms, and X is CH ₂ -CH ₂ , CH = CH or C≡C, Y ¹ each independently represents that it can be selected from a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 1 to 10 carbon atoms Oxy, hydroxyl, cyano, dialkylamino (alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms The following formulas Y ¹ -1 to Y ¹ -6 substituted by straight or branched fluorenyl, carboxyl, aldehyde, and nitro substituents having 1 to 10 carbon atoms (where ** represents a bond with X Position, *** indicates the bonding position with Y ² ), Y ² indicates -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ³ or -O-CO-CR ⁵ = CR ⁶ -Y ³ , R ³ and R ⁴ are independently represented as hydrogen atom or methyl group, R ⁵ and R ⁶ are independently represented as hydrogen atom or methyl group, Y ³ is independently Li stands for 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. (Alkyl groups are each independently a linear or branched alkyl group having 1 to 10 carbon atoms), a linear or branched ester group having 1 to 10 carbon atoms, and a linear or branched chain having 1 to 10 carbon atoms (Phenyl, biphenyl, naphthyl, alicyclic hydrocarbons having 5 to 8 carbon atoms, phenyl-cyclohexyl, or cyclohexyl-phenyl) substituted with fluorenyl, carboxyl, aldehyde, and nitro substituents)     The composition according to claim 1, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement.     The composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain selected from any one grouped by the following formulae (1) to (6), (wherein A and B And D are independently represented as single bonds, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O -CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to these may be replaced by a halogen group; T is a single bond or an alkylene group having 1 to 12 carbon atoms And the hydrogen atom bonded to these may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic ring having 5 to 8 carbon atoms; The ring of the formula hydrocarbon, or the same or different 2 to 6 rings selected from these substituents is a group formed by a bonding group B, and the hydrogen atom systems bonded to these may be independently independent -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group , C1-C5 alkyl group, or C1-C5 alkoxy group; Y ₂ is selected from bivalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon number 5 ~ 8 alicyclic hydrocarbons, and combinations thereof Groups of bases, hydrogen atoms bonded to these can be independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, 1 to 5 carbon atoms Alkyl or alkoxy having 1 to 5 carbons; R is hydroxy, alkoxy having 1 to 6 carbons, or has 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 = CH-, when the number of X is 2, X may be the same as or different from each other; Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkoxy 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 each 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 the like The base of the group formed by combination; however, if X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is aromatic Ring, if the number of P is 2 or more, P may be the same as or different from each other; if the number of Q is 2 In the above, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, A is also expressed as a single bond when T is a single bond; when l1 is 1, When T is a single bond, B is also represented as a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof) The composition according to any one of claims 1 to 3, wherein the component (A) has a liquid crystal side chain selected from any one grouped by the following formulae (21) to (31), (wherein A and B have the same definitions as above; Y ₃ is selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. , And the groups formed by these combinations, and the hydrogen atom systems bonded to these can be independently -NO ₂ , -CN, halogen groups, alkyl groups having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. R ₃ represents hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, monovalent benzene ring, naphthalene ring, Benzene ring, furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; one of q1 and q2 is 1 , The other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more, in formula (25) ~ (26), the total of all m or more 1, m1, m2 and m3 each independently represents an integer of lines 1 to 3; R ₂ represents a hydrogen atom based, -NO _2, -CN, halo A divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a heterocyclic ring containing nitrogen and carbon atoms, alicyclic hydrocarbon having 5 to 8, and alkyl, or alkoxy; Z _1, Z ₂ are diagrams Single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- )     A method for manufacturing a substrate with a liquid crystal alignment film is to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided by having the following steps: [I] Any one of claims 1 to 4 A step of applying a composition to a substrate having a conductive film for lateral electric field driving to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] applying [II] The obtained coating film is subjected to a heating step.         A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by the method according to claim 5.         A lateral electric field drive type liquid crystal display element having a substrate as claimed in claim 6.         A method for manufacturing a liquid crystal display element is to obtain a lateral electric field drive type liquid crystal display element by having the following steps: a step of preparing a substrate (first substrate) as claimed in claim 6; and obtaining a second substrate having a liquid crystal alignment film This step is to obtain a liquid crystal alignment film having an alignment control capability by the following steps: [I '] Applying the polymer composition according to any one of claims 1 to 17 on a second substrate to form a coating. A film step; [II '] a step of irradiating polarized ultraviolet rays on the coating film obtained by [I']; and [III '] a step of heating the coating film obtained by [II']; and [IV] so that The liquid crystal alignment films of the first and second substrates face each other with liquid crystals interposed therebetween, and the first and second substrates are arranged opposite to each other to obtain a liquid crystal display element.         A lateral electric field driving type liquid crystal display device is manufactured by the method as claimed in claim 8.     A compound represented by the following formula (am1) (in the formula (am1), PL represents a polymerizable group and is selected from polymerizable groups grouped by the following formulas PL-1 to PL-5, and the formula PL In -1 to PL-5, R ¹ and R ² and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms substituted with halogen. Or branched alkyl (* indicates the bonding position with L), L is a straight or branched alkylene group having 1 to 16 carbons, and X is CH ₂ -CH ₂ , CH = CH or C ≡C, Y ¹ each independently represents a group selected from 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, and a cyanide Group, dialkylamino group (alkyl groups are each independently a straight or branched alkyl group having 1 to 10 carbon atoms), a straight or branched ester group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms The following formula Y ¹ -1 to Y ¹ -6 substituted by the substituents of a straight-chain or branched fluorenyl group, carboxyl group, aldehyde group and nitro group (** indicates the bonding position with X, *** Indicates the bonding position with Y ² ), Y ² indicates -COOH, -CR ³ = CR ⁴ -COOH, -CR ⁵ = CR ⁶ -CO-OY ³ or -O-CO-CR ⁵ = CR ^6- Y ^3, R ³ and R ⁴ each independently represent lines of Atom or a methyl group, R ⁵ and R ⁶ each independently represent a hydrogen based atom or a methyl group, Y ³ each independently represent lines which may be selected from halogen group, a C 1-4 straight-chain or branched alkyl group having 1 to 10 carbon 1 to 10 linear or branched alkoxy, hydroxyl, cyano, dialkylamino (alkyl groups are each independently a straight or branched alkyl having 1 to 10 carbons), carbon number 1 to 10 linear or branched ester groups, 1 to 10 carbon or straight chain or branched fluorenyl, carboxyl, aldehyde, and nitro substituents substituted with phenyl, biphenyl, naphthalene Group, alicyclic hydrocarbon having 5 to 8 carbon atoms, phenyl-cyclohexyl or cyclohexyl-phenyl)