WO2023171760A1

WO2023171760A1 - Phase difference film composition and single-layer phase difference material

Info

Publication number: WO2023171760A1
Application number: PCT/JP2023/009103
Authority: WO
Inventors: 友基玉井; ダニエルアントニオ櫻葉汀; 司藤枝; 隆之根木
Original assignee: 日産化学株式会社
Priority date: 2022-03-10
Filing date: 2023-03-09
Publication date: 2023-09-14

Abstract

Provided, as a phase difference film composition that enables production of a single-layer phase difference material having a high phase difference value an an NZ coefficient such that 0.4 ≤ NZ ≤ 0.6 by a simpler process, a phase difference film composition including (A) a side-chain-type polymer having a side chain having a photoreactive portion represented by formula (a) and a side chain having a portion represented by formula (b), and (B) an organic solvent. Also provided is a single-layer phase difference material obtained from the abovementioned polymer composition.

Description

Composition for retardation film and single layer retardation material

The present invention relates to a composition for a retardation film and a single-layer retardation material. Specifically, the material has optical properties suitable for use in display devices, recording materials, etc., and in particular, can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays and organic EL (Electro Luminescence) display devices. The present invention relates to a liquid crystalline polymer, a composition containing the polymer, and a single-layer retardation material obtained from the composition.

Due to demands for improved display quality and weight reduction of liquid crystal display devices and organic EL display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. ing. In order to meet this demand, films have been developed that utilize the optical anisotropy of polymerizable liquid crystal compounds. The polymerizable liquid crystal compound used here generally has a polymerizable group and a liquid crystal structure site (a structure site having a spacer part and a mesogen part), and an acrylic group is widely used as this polymerizable group. ing.

Such polymerizable liquid crystal compounds are generally made into polymers (films) by polymerizing them by irradiating them with radiation such as ultraviolet rays. For example, a method of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acrylic group between aligned supports and irradiating the compound with radiation while maintaining the compound in a liquid crystal state (Patent Document 1); There is a known method (Patent Document 2) in which a photopolymerization initiator is added to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group or a composition in which a chiral liquid crystal is mixed with this mixture, and the mixture is irradiated with ultraviolet rays to obtain a polymer. It is being

In addition, oriented films using polymerizable liquid crystal compounds or polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4), oriented films using polymers containing photocrosslinking sites (Patent Documents 5 and 6), etc. Various single layer coated oriented films have been reported.

Organic EL panels have a reflective metal layer and are prone to problems with external light reflection. Therefore, it is known that these problems can be prevented by providing a circularly polarizing plate composed of a linearly polarizing plate and a retardation plate (film). However, when a conventional retardation plate is used as a circularly polarizing plate, there is a problem in that the antireflection of external light in an oblique direction is insufficient and undesirable coloring occurs.

Here, there is an NZ coefficient as a parameter representing the characteristics of the retardation film. The NZ coefficient is calculated using the formula {NZ=(nx nz), where nx is the refractive index of the slow axis in the plane of the retardation film, ny is the refractive index of the fast axis, and nz is the refractive index in the thickness direction of the film. /(nx ny)}. The closer this NZ coefficient is to 0.5, the less the viewing angle dependence of the retardation value of the retardation film becomes, and the more the effect of preventing reflection of external light in an oblique direction in a circularly polarizing plate of an organic EL is improved.

Japanese Unexamined Patent Publication No. 62-70407 Japanese Patent Application Publication No. 9-208957 European Patent Application No. 1090325 International Publication No. 2008/031243 Japanese Patent Application Publication No. 2008-164925 Japanese Patent Application Publication No. 11-189665

The present invention was made in view of the above problems, and enables the production of a single-layer retardation material with an NZ coefficient of 0.4 ≦ NZ ≦ 0.6 and a high retardation value through a simpler process. The present invention aims to provide a composition for a retardation film and a single-layer retardation material obtained from the composition.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a composition containing a specific polymer, the NZ coefficient can be reduced to 0.4 ≦ NZ ≦ without using a liquid crystal alignment film. 0.6, and it was discovered that a single-layer retardation material having a high refractive index anisotropy (Δn) can be obtained in a thin film, and the present invention was completed.

Therefore, the present invention provides the following composition for a retardation film and a single-layer retardation material.
<1> (A) A structure that has a terminal carboxylic acid side chain having a photoreactive site and two or more aromatic ring structures, and the two rings on the terminal side are not covalently bonded by a single bond. A composition for a retardation film comprising a side chain type copolymer containing a terminal carboxylic acid side chain, and (B) an organic solvent.
<2> The side chain type copolymer (A) has a side chain having a photoreactive site represented by the following formula (a) and a side chain having a site represented by the following formula (b). The composition for a retardation film according to <1>, which is a chain polymer.

(In the formula, R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with ^a fluorine atom or an organic group. -CH ₂ CH ₂ - may be substituted with -CH=CH-, and -CH ₂ - in R ¹ may be substituted with -O-, -NH-C(=O)-, -C(= O) -NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- may be substituted with a group selected from the group consisting of: However, adjacent --CH ₂ -- groups are not substituted with these groups at the same time.
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group.
R ³ is a single bond, -CH ₂ -, -O-, -C(=O)-O-, -OC(=O)- or -CH=CH-C(=O)-O- be.
R ⁴ is a divalent aromatic group, -Ph-Cy-, -Cy-Ph-, or a divalent fused cyclic group (where Ph represents a phenylene group and Cy represents a cyclohexanediyl group). be.
R ⁵ is -CH ₂ -, -O-, -NH-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CH=CH- C(=O)-O-, -C(=O)-NH-, -NH-C(=O)- or -NH-C(=O)-NH-.
R ⁶ is an alkylene group having 1 to 10 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Furthermore, -CH ₂ - in R ⁶ may be substituted with a group selected from the group consisting of -O-, -NH- and -C(=O)-. Adjacent --CH ₂ -- groups may be substituted with these groups at the same time.
The hydrogen atom in the ring structure and CH═CH structure in formula (a) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a halogen group, a cyano group, and a nitro group.
The hydrogen atom in the ring structure in formula (b) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms. , a halogen group, a cyano group, and a nitro group.
When two or more R ² , R ³ , R ⁴ or R ⁵ are present, the plurality of R ² , R ³ , R ⁴ or R ⁵ may be the same or different.
a is 0, 1 or 2.
b is 0 or 1.
c is an integer satisfying 0≦c≦2b+4.
d is 1 or 2.
e is 0 or 1.
f is 0 or 1.
The broken lines are bonds. )
<3> The composition for a retardation film according to <2>, wherein the side chain having a photoreactive site represented by the above formula (a) is represented by the following formula (a1).

(In the formula, R ¹ , R ² and a are the same as above.
R ^3A is a single bond, -O-, -C(=O)-O- or -OC(=O)-. When two or more R ^3As exist, the plural R ^3As may be the same or different.
The hydrogen atom in the benzene ring and in the CH═CH structure in formula (a1) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a halogen group, a cyano group, and a nitro group.
The broken lines are bonds. )
<4> The polymer composition and composition for a retardation film according to <2> or <3>, wherein the number of ring structures in the side chain represented by the above formula (b) is 3 or less.
<5> The composition for a retardation film according to any one of <1> to <4>, wherein the side chain polymer exhibits liquid crystallinity.
<6> (I) A step of applying the retardation film composition according to any one of <1> to <5> onto a substrate to form a coating film,
(II) A method for producing a single-layer retardation material, comprising the steps of: (II) irradiating the coating film with polarized ultraviolet rays; and (III) heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.
<7> A single-layer retardation material obtained from the composition according to any one of <1> to <5>.

According to the present invention, it is possible to provide a single-layer retardation material having an NZ coefficient of 0.4 ≦ NZ ≦ 0.6 and a high retardation value even if it is a thin film, and a polymer that provides the same.

As a result of intensive research, the present inventors obtained the following knowledge and completed the present invention.
The composition for a retardation film of the present invention (hereinafter also referred to as a polymer composition) has a photosensitive side chain type polymer (hereinafter also simply referred to as a side chain type polymer) capable of exhibiting liquid crystallinity. The coating film obtained using the above polymer composition is a film containing a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. This coating film is subjected to orientation treatment by polarized light irradiation without performing rubbing treatment. After irradiation with polarized light, the side chain type polymer film is heated to become a film imparted with optical anisotropy (hereinafter also referred to as a single-layer retardation material). At this time, the slight anisotropy developed by polarized light irradiation becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, highly efficient alignment treatment can be achieved as a single-layer retardation material, and a single-layer retardation material imparted with high optical anisotropy can be obtained.

In addition, in the polymer composition of the present invention, the side chain type polymer includes a side chain of a terminal carboxylic acid having a photoalignable site, typified by a side chain represented by the above formula (a), and a side chain of a terminal carboxylic acid represented by the above formula (a). A terminal carboxylic acid that has two or more aromatic ring structures, as represented by the side chain represented by (b), and has a structure in which the two rings on the terminal side are single bonds and are not covalently bonded. By including the side chains, the ring structures of the two rings are on the same plane and the interaction between the side chains is strengthened, which increases liquid crystallinity and photoalignment, promoting alignment in the slow axis direction in the plane. At the same time, the disturbance in the orientation in the depth direction is reduced. As a result, the retardation material obtained from the polymer composition of the present invention exhibits a high retardation value even in a thin film, nx is larger than nz, and due to the effect of the terminal carboxylic acid, nz is approximately equal to nx and ny. Indicates an intermediate value. Note that these include the inventor's opinion regarding the mechanism of the present invention, and do not constrain the present invention.

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

[Polymer composition]
The polymer composition of the present invention is characterized by containing (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range and (B) an organic solvent.

[(A) Side chain type polymer]
Component (A) is a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and has two or more rings and a terminal carboxylic acid side chain having a photoreactive site. It is also a side chain type copolymer containing a terminal carboxylic acid side chain in which the two rings on the terminal side have a single bond and are not covalently bonded. The above-mentioned side chain type copolymer has a side chain having a photoreactive moiety represented by the following formula (a) (hereinafter also referred to as side chain a) and a moiety having a photoreactive moiety represented by the following formula (b). A side chain type polymer having a side chain (hereinafter also referred to as side chain b) is preferred.

In formula (a), R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Furthermore, -CH ₂ CH ₂ - in R ¹ may be substituted with -CH=CH-, and -CH ₂ - in R ¹ may be substituted with -O-, -NH-C(=O)- , -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C( It may be substituted with a group selected from the group consisting of =O)-. However, adjacent --CH ₂ -- groups are not substituted with these groups at the same time.
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group.
R ³ is a single bond, -CH ₂ -, -O-, -C(=O)-O-, -OC(=O)- or -CH=CH-C(=O)-O- be.
The hydrogen atom in the ring structure and CH═CH structure in formula (a) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a halogen group, a cyano group, and a nitro group.
When two or more R ² or R ³ are present, the plurality of R ² or R ³ may be the same or different.
a is 0, 1 or 2.
b is 0 or 1.
c is an integer satisfying 0≦c≦2b+4.
The broken lines are bonds.

In formula (b), R ¹ has the same definition as R ¹ in formula (a), and R ⁴ is a divalent aromatic group, -Ph-Cy-, -Cy-Ph-, or a divalent condensed group. It is a cyclic group (where Ph represents a phenylene group and Cy represents a cyclohexanediyl group).
R ⁵ is -CH ₂ -, -O-, -NH-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CH=CH- C(=O)-O-, -C(=O)-NH-, -NH-C(=O)- or -NH-C(=O)-NH-.
R ⁶ is an alkylene group having 1 to 10 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Furthermore, -CH ₂ - in R ⁶ may be substituted with a group selected from the group consisting of -O-, -NH- and -C(=O)-. Adjacent --CH ₂ -- groups may be substituted with these groups at the same time.
The hydrogen atom in the ring structure in formula (b) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms. , a halogen group, a cyano group, and a nitro group.
When two or more R ⁴ or R ⁵ are present, the plurality of R ⁴ or R ⁵ may be the same or different.
d is 1 or 2.
e is 0 or 1.
f is 0 or 1.
The broken lines are bonds.

The alkylene group having 1 to 30 carbon atoms represented by R ¹ may be linear, branched, or cyclic, and specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9 -diyl group, decane-1,10-diyl group, etc.

Examples of the divalent aromatic group represented by R ² include a phenylene group and a biphenylylene group. Examples of the divalent alicyclic group represented by R ² include a cyclohexanediyl group. Examples of the divalent heterocyclic group represented by R ² include furandiyl group. The divalent condensed cyclic group represented by R ² includes a naphthylene group and the like.

Examples of the divalent aromatic group represented by R ⁴ include a phenylene group and a biphenylylene group. The divalent condensed cyclic group represented by R ⁴ includes a naphthylene group and the like.

The alkylene group having 1 to 10 carbon atoms represented by R ⁶ may be linear, branched, or cyclic, and specific examples include the groups listed as specific examples of R ¹ above.

The side chain a is preferably one represented by the following formula (a1) (hereinafter also referred to as side chain a1).

In formula (a1), R ¹ , R ² and a are the same as above. R ^3A is a single bond, -O-, -C(=O)-O- or -OC(=O)-. When two or more R ^3As exist, the plural R ^3As may be the same or different. The hydrogen atom in the benzene ring and in the CH═CH structure in formula (a1) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a cyano group, and a nitro group. The broken lines are bonds.

As the side chain a1, for example, one represented by the following formula (a1-1) is preferable.

In formula (a1-1), L is a linear or branched alkylene group having 1 to 16 carbon atoms. X is a single bond, -O-, -C(=O)-O-, or -OC(=O)-.

(A) The side chain type polymer is preferably one that reacts with light in a wavelength range of 250 to 400 nm and exhibits liquid crystallinity in a temperature range of 100 to 300°C. (A) The side chain type polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 to 400 nm.

(A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction or an isomerization reaction in response to light. The structure of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogenic component. When the above-mentioned side chain type polymer is used as a single layer retardation material, stable optical anisotropy can be obtained.

More specific examples of structures of photosensitive side chain polymers that can exhibit liquid crystallinity include (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, It is preferable that the structure has a main chain composed of at least one member selected from the group consisting of a radically polymerizable group such as norbornene and siloxane, and a side chain a.

The number of ring structures in the side chain represented by the above formula (b) is preferably 3 or less. Here, the ring structure of the condensed ring is counted as one. That is, the number of ring structures in a phenylene group or a naphthylene group is one, and the number of ring structures in a biphenylylene group or a cyclohexanediyl group is two.

As the side chain b, for example, one represented by the following formula (b1) is preferable.

In formula (b1), R ¹ , R ⁴ to R ⁶ , d and f are the same as above. The number of ring structures in formula (b1) is three or less. The hydrogen atom in the benzene ring in formula (b1) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms. , a halogen group, a cyano group, and a nitro group. The broken lines are bonds.

Furthermore, since the side chain type polymer (A) exhibits liquid crystallinity in a temperature range of 100 to 300°C, it is preferable that it further has a side chain (hereinafter also referred to as side chain c) that exhibits only liquid crystallinity. . Note that "expressing only liquid crystallinity" here means that a polymer having only side chain c is used during the production process of the retardation material of the present invention (i.e., steps (I) to (III) described below). This means that it does not exhibit photo-alignment properties and only exhibits liquid crystallinity.

The side chain c is preferably one or more liquid crystalline side chains selected from the group consisting of the following formulas (1) to (12).

In formulas (1) to (12), A ¹ and A ² each independently represent a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O) -, -C(=O)-NH- or -NH-C(=O)-. When two or more A ² 's exist, the plural A ² 's may be the same or different from each other. R ¹¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon It is an alkyl group having 1 to 12 carbon atoms or an alkyloxy group having 1 to 12 carbon atoms. R ¹² is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these The hydrogen atom bonded to these may be substituted with -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ¹³ is a hydrogen atom, -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon having 5 to 8 carbon atoms group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. E is -C(=O)-O- or -OC(=O)-. d is an integer from 1 to 12. k1 to k5 are each independently an integer of 0 to 2, but the total of k1 to k5 is 2 or more. k6 and k7 are each independently an integer of 0 to 2, but the sum of k6 and k7 is 1 or more. m1, m2 and m3 are each independently an integer of 1 to 3. n is 0 or 1. Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ O- or -CF ₂ -. The broken lines are bonds.

Among these, the side chain c is preferably one represented by any one of formulas (1) to (11).

The side chain type polymer of component (A) has a monomer having a structure represented by formula (a), a monomer having a structure represented by formula (b), and, if desired, a structure that exhibits only liquid crystallinity. It can be obtained by polymerizing monomers.

Examples of the monomer having the structure represented by formula (a) (hereinafter also referred to as monomer M1) include a compound represented by formula (M1) below.

(In the formula, R ¹ , R ² , R ³ , a and m are the same as above. The hydrogen atom in the ring structure and CH=CH structure in the formula is an alkyl group having 1 to 6 carbon atoms, (Optionally substituted with a substituent selected from a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen group, a cyano group, and a nitro group.)

As the monomer M1, one represented by the following formula (M1A) is preferable.

(In the formula, R ¹ , R ² , R ^3A , R and a are the same as above. The hydrogen atom in the ring structure and CH=CH structure in the formula is an alkyl group having 1 to 6 carbon atoms, (Optionally substituted with a substituent selected from a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen group, a cyano group, and a nitro group.)

Among the monomers M1A, those represented by the following formula (M1B) are more preferable.

(In the formula, L and X are the same as above.)

In formulas (M1), (M1A) and (M1B), PL is a polymerizable group represented by any of the following formulas (PL-1) to (PL-5).

In formulas (PL-1) to (PL-5), Q ¹ , Q ² and Q ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen A linear or branched alkyl group having 1 to 10 carbon atoms substituted with The broken line is a bond with R ¹ or L. Some of these monomers are commercially available, and others can be produced from known substances by known production methods.

Preferred examples of the monomer M1 include those represented by the following formulas (M1-1) to (M1-5).

(In the formula, PL is the same as above. p is an integer from 2 to 9.)

Examples of the monomer having the structure represented by formula (b) (hereinafter also referred to as monomer M2) include compounds represented by formula (M2) below.

(In the formula, PL, R ¹ , R ⁴ to R ⁶ , d, e, and f are the same as above. The hydrogen atom in the ring structure in the formula is an alkyl group having 1 to 6 carbon atoms, 6 haloalkyl group, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen group, a cyano group, and a nitro group.)

The monomer M2 is preferably one represented by the following formula (M2A).

(In the formula, PL, R ¹ , R ⁴ to R ⁶ , d and f are the same as above. The hydrogen atom in the benzene ring in the formula is an alkyl group having 1 to 6 carbon atoms, It may be substituted with a substituent selected from a haloalkyl group, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen group, a cyano group, and a nitro group.)

As the monomer M2, monomers represented by the following M2-1 to M2-6 are preferable.

(In the formula, PL and p are the same as above.)

Some of these monomers are commercially available, and some can be produced from known substances by known production methods.

There are no particular limitations on the method for synthesizing (M2-1) to (M2-6). For example, as shown in the following formula, M3-1 is synthesized according to the synthesis method described in JP-A-9-118717, and acid chloride (M2-1-1) is obtained using thionyl chloride or oxalyl chloride. be able to. Subsequently, M2-1-3 is obtained by condensing the carboxylic acid terminal-protected compound (M2-1-2) and the acid chloride (M2-1-1) in the presence of a base such as triethylamine. I can do it. As the protecting group (PG), a tert-butyl group, a monomethoxymethyl group, etc. can be used. M2-1 can be produced by deprotecting the protecting group (PG) of M2-1-3 with an acid.

A monomer having a structure that exhibits only liquid crystallinity (hereinafter also referred to as monomer M3) is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at the side chain site. That's true.

The mesogenic group having a side chain may be a group that forms a mesogenic structure by itself, such as biphenyl or phenylbenzoate, or a group that forms a mesogenic structure by hydrogen bonding between side chains, such as benzoic acid. Good too. The mesogenic group included in the side chain preferably has the following structure.

More specific examples of monomer M3 include hydrocarbons, radically polymerizable groups such as (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane. It is preferable that the structure has a polymerizable group derived from at least one selected from the group and at least one of the above formulas (1) to (12). In particular, the monomer M3 preferably has (meth)acrylate as a polymerizable group, and preferably has a side chain terminal of -COOH.

Preferred examples of monomer M3 include those represented by the following formulas (M3-1) to (M3-9).

(In the formula, PL and p are the same as above.)

In addition, other monomers can be copolymerized within a range that does not impair the ability to develop photoreactivity and/or liquid crystallinity. Other monomers include, for example, industrially available monomers capable of radical polymerization. Specific examples of other monomers include unsaturated carboxylic acids, acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

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

Examples of acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl acrylate. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Examples include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like. Examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, and the like. Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

From the viewpoint of photoreactivity, the content of side chain a in the side chain type polymer of the present invention is preferably 5 to 90 mol%, more preferably 5 to 80 mol%, and even more preferably 5 to 50 mol%.

The content of side chain b in the side chain type polymer of the present invention is preferably 10 to 95 mol%, more preferably 5 to 70 mol%, and even more preferably 10 to 70 mol%, from the viewpoint of retardation value.

From the viewpoint of retardation value, the content of side chain c in the side chain type polymer of the present invention is defined as the content of side chain c in the case where the total content of side chain a and side chain b is less than 100 mol%. It is preferably 10 to 100 mol%.

The side chain type polymer of the present invention may contain other side chains as described above. The content of other side chains is the remaining portion when the total content of side chains a to c is less than 100 mol%.

The method for producing the side chain type polymer of component (A) is not particularly limited, and general industrially used methods can be used. Specifically, it can be produced by radical polymerization, cationic polymerization, or anionic polymerization using the vinyl groups of monomer M1, monomer M2, optionally monomer M3, and optionally other monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.

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

A radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) ), alkyl peresters (peroxyneodecanoic acid tert-butyl ester, peroxypivalic acid tert-butyl ester, peroxy 2-ethylcyclohexanoic acid tert-amyl ester, etc.), persulfates (potassium persulfate, (sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.), and the like. The radical thermal polymerization initiators may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3' , 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4- [p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s- Triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2 -Methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenylketone, bis(5-2,4-cyclo Pentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone , 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4 '-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2 -(3-Methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1- Examples include (2-benzoyl)ethanone. The radical photopolymerization initiators may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced polymer. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, and tetramethylurea. , pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve Acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert -Butyl ether, 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, Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, Examples include 3-ethoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide.

The above organic solvents may be used alone or in combination of two or more. Furthermore, even a solvent that does not dissolve the produced polymer may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. Further, in radical polymerization, oxygen in an organic solvent becomes a cause of inhibiting the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.

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

In the radical polymerization reaction described above, if the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer will be small, and if it is small, the molecular weight of the obtained polymer will be large. The amount is preferably 0.1 to 10 mol % based on the monomer to be polymerized. Furthermore, various monomer components, solvents, initiators, etc. can be added during polymerization.

In order to recover the polymers produced from the reaction solution obtained by the above reaction, the reaction solution may be poured into a poor solvent to precipitate the polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, and the like. The polymer precipitated in a poor solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating. Further, by repeating the operation of redissolving the recovered polymer in an organic solvent and reprecipitation recovery 2 to 10 times, the amount of impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more kinds of poor solvents selected from these, since the efficiency of purification will further increase.

The side chain type polymer (A) of the present invention has a weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, considering the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film. is preferably from 2,000 to 2,000,000, more preferably from 2,000 to 1,000,000, even more preferably from 5,000 to 200,000.

[(B) Organic solvent]
The organic solvent of component (B) is not particularly limited as long as it can dissolve the polymer component. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-Butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, Diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl Examples include ether. These may be used alone or in combination of two or more.

[Other ingredients]
The polymer composition of the present invention may contain components other than components (A) and (B). Examples include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the retardation material and the substrate. Not limited.

Specific examples of solvents (poor solvents) that improve film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol. , ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3 -Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, Propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate , n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, etc. Examples include solvents having low surface tension.

These poor solvents may be used alone or in combination of two or more. When using the above poor solvent, its content is preferably 5 to 80% by mass in the solvent, and 20 to 60% by mass so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. It is more preferable that it is mass %.

Compounds that improve film thickness uniformity and surface smoothness include fluorosurfactants, silicone surfactants, nonionic surfactants, and the like. Specific examples of these include FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, F560, F563, R-30, R-40, R- 41 (manufactured by DIC), Florado FC430, FC431 (manufactured by 3M), Asahi Guard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) and the like. The content of these surfactants is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of component (A).

Specific examples of compounds that improve the adhesion between the retardation material and the substrate include functional silane-containing compounds, such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. , 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane , 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-(3-triethoxysilane) silyl)propyltriethylenetetramine, N-(3-trimethoxysilyl)propyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9 -trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Examples include ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

Furthermore, in addition to improving the adhesion between the substrate and the retardation material, phenoplast compounds and epoxy group-containing compounds are added to the polymer composition to prevent deterioration of characteristics due to backlight when forming a polarizing plate. May be added.

Specific examples of phenoplast additives are shown below, but are not limited thereto.

Specific examples of epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. can be mentioned.

When using a compound that improves adhesion to the substrate, its content is preferably 0.1 to 30 parts by mass, and 1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the polymer composition. is more preferable. If the content is less than 0.1 part by mass, no effect of improving adhesion can be expected, and if the content is more than 30 parts by mass, the alignment of the liquid crystal may deteriorate.

A photosensitizer can also be used as an additive. As the photosensitizer, colorless sensitizers and triplet sensitizers are preferred.

Examples of photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, aromatic 2-hydroxy Ketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3-methyl-β- Naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline , 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3 -methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene) )-3-Methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenoyl methylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4 , 6-trinitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthene, etc.), 2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone, etc.), naphthalene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merocoumarin, etc. can be mentioned. Among these, aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal are preferred.

In addition to the above-mentioned materials, the polymer composition of the present invention may also contain dielectric materials for the purpose of changing the electrical properties such as permittivity and conductivity of the retardation material, as long as the effects of the present invention are not impaired. A crosslinkable compound may be added for the purpose of increasing the hardness and density of a conductive substance and, furthermore, a film when used as a retardation material.

[Preparation of polymer composition]
The polymer composition of the present invention is preferably prepared as a coating liquid so as to be suitable for forming a single-layer retardation material. That is, the polymer composition used in the present invention contains component (A), a solvent or compound that improves the film thickness uniformity and surface smoothness, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, etc. Preferably, the component (B) is prepared as a solution dissolved in an organic solvent. Here, the content of component (A) in the composition of the present invention is preferably 1 to 30% by mass, more preferably 5 to 30% by mass.

In addition to the polymer of component (A), the polymer composition of the present invention may contain other polymers as long as they do not impair the ability to develop liquid crystals and photosensitivity. At this time, the content of other polymers in the polymer component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass. Examples of other polymers include polymers that are not photosensitive side-chain polymers that can exhibit liquid crystallinity, such as poly(meth)acrylate, polyamic acid, and polyimide.

[Single layer retardation material]
The single-layer retardation material of the present invention can be manufactured by a method including the following steps (I) to (III).
(I) a step of applying the composition of the present invention onto a substrate to form a coating film;
(II) a step of irradiating the coating film with polarized ultraviolet rays; and (III) a step of heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.

[Step (I)]
Step (I) is a step of applying the composition of the present invention onto a substrate to form a coating film. More specifically, the composition of the present invention can be applied to substrates (e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, metal (e.g., aluminum, molybdenum, chromium, etc.) coated substrates, glass substrates, quartz substrates). , ITO substrate, etc.) or films (e.g., resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.), bar coat, spin coat, flow coat, roll coat. , slit coating, slit coating followed by spin coating, inkjet method, printing method, etc. After coating, the solvent can be evaporated at 50 to 200°C, preferably 50 to 150°C using a heating means such as a hot plate, hot air circulation oven, or IR (infrared) oven to obtain a coating film.

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

The amount of polarized ultraviolet radiation depends on the coating used. The irradiation amount is 1 to 70% of the amount of polarized ultraviolet light that achieves the maximum value of ΔA, which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in a direction perpendicular to the polarization direction of the coating film. It is preferably within the range of , and more preferably within the range of 1 to 50%.

[Step (III)]
In step (III), the coating film irradiated with polarized ultraviolet rays in step (II) is heated. By heating, orientation controllability can be imparted to the coating film.

For heating, heating means such as a hot plate, hot air circulation type oven, IR (infrared rays) type oven, etc. 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 the temperature range at which the polymer of component (A) contained in the composition of the present invention develops liquid crystallinity (hereinafter referred to as liquid crystal development temperature). In the case of a thin film surface such as a paint film, the temperature at which liquid crystals appear on the surface of the paint film is expected to be lower than the temperature at which liquid crystals appear when the polymer of component (A) is observed in bulk. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystal development temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is a temperature that is 10°C lower than the lower limit of the liquid crystal development temperature range of the polymer of component (A), and a temperature that is 10°C lower than the upper limit of the liquid crystal temperature range. It is preferable that the temperature is within a range with an upper limit of . If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high than the above temperature range, the condition of the coating film tends to be insufficient. tends to be close to an isotropic liquid state (isotropic phase), in which case it may be difficult to reorient in one direction due to self-organization.

The liquid crystal development temperature is the liquid crystal transition temperature at which the polymer or coating surface undergoes a phase transition from a solid phase to a liquid crystal phase, and is an isotropic phase at which a phase transition occurs from a liquid crystal phase to an isotropic phase. A temperature below the phase transition temperature (Tiso). For example, expressing liquid crystallinity at 130°C or lower means that the liquid crystal transition temperature at which a phase transition from a solid phase to a liquid crystal phase occurs is 130°C or lower.

The thickness of the coating film formed after heating can be appropriately selected in consideration of the level difference and optical properties of the substrate used, and is preferably 0.5 to 10 μm, for example.

The thin film obtained from the composition for retardation film of the present invention has an NZ coefficient of 0.4 ≦ NZ ≦ 0.6, preferably 0.41 ≦ NZ ≦ 0.58, and even if it is a thin film, the retardation value It is possible to provide a single-layer retardation material with high retardation.

The single-layer retardation material of the present invention thus obtained is a material having optical properties suitable for use in display devices, recording materials, etc., and is particularly suitable for polarizing plates and retardation plates for liquid crystal displays and organic EL. It is suitable as an optical compensation film such as.

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples, Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

Monomers MA1, MB1 to MB6, MC1 to MC3, and MD1 used in Examples are shown below.
MA1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. MB1 and MC2 were synthesized according to the synthesis method described in International Publication No. 2017/135130.
MB3 was synthesized according to the synthesis method described in International Publication No. 2014/054785.
MB6 was synthesized according to the synthesis method described in JP-A-2016-128403.
MC1 was synthesized according to the synthesis method described in JP-A-9-118717.
MC3 was synthesized according to the synthesis method described in JP-A-2009-19117.
MD1 was synthesized according to the synthesis method described in JP-A-2012-27354.
MB2, MB4, and MB5 are new compounds, and the synthesis method is shown below.
In addition, the side chain derived from MA1 corresponds to side chain a, the side chain derived from MB1 to MB6 corresponds to side chain b, the side chain derived from MC1 to MC3 corresponds to side chain c, and the side chain derived from MB1 to MB6 corresponds to side chain c. The derived side chain does not correspond to any of side chain a, side chain b, and side chain c.

In addition, the abbreviations of reagents used in this example are shown below.
(organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve CPN: Cyclopentanone THF: Tetrahydrofuran DMF: N,N-dimethylformamide THF: Tetrahydrofuran MeCN: Acetonitrile PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate DMAc: N , N-dimethylacetamide (polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile (surfactant)
R40: Megafac R-40 (manufactured by DIC)
F563: Megafac F-563 (manufactured by DIC)

< ^1H -NMR measurement>
Equipment: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz.
Solvent: Deuterated dimethyl sulfoxide (DMSO-d ₆ ).
Standard material: Tetramethylsilane (TMS).

[1] Synthesis of monomer <<Synthesis of MB2>>

<Synthesis of [MB2-1] and [MB2-2]>
In a 3,000 mL four-necked flask, add DMAc (400 g), ethyl 4-hydroxy-3-methoxybenzoate (100 g, 510 mmol), potassium carbonate (98.6 g, 714 mmol), and potassium iodide (8.46 g, 51 g). 0 mmol) was added thereto, and 6-chloro-1-hexanol (83.6 g, 612 mmol) was added dropwise over 2 hours under heating conditions of 85°C. After dropping, the mixture was reacted at the same temperature for 22 hours to eliminate the raw materials. After the reaction was completed, the mixture was diluted with ethyl acetate (1200 g), and the organic phase was washed three times with pure water. Subsequently, the organic phase was collected and concentrated under reduced pressure to obtain [MB2-1] as a crude product.
Methanol (MeOH, 300 g), pure water (225 g), and potassium hydroxide (50.5 g) were added to the obtained crude [MB2-1], and the mixture was reacted at 40° C. for 3 hours. After the reaction was completed, a 3.0 mol/L aqueous hydrochloric acid solution was added to the reaction solution to precipitate crystals, and the crystals were collected by filtration. Subsequently, the obtained crystals were slurry washed with pure water (500 g), then slurry washed with MeCN (250 g), and the filtered material was dried under reduced pressure to obtain 124 g (white crystals) of [MB2-2] ( Yield: 91%).

<Synthesis of [MB2-3], [MB2-4], [MB2-5]>
THF (494 g), [MB2-2] (82.3 g, 307 mmol), and triethylamine (Et ₃ N, 80.0 g, 790 mmol) were placed in a 2,000 mL four-neck flask, and the mixture was heated under ice-cooled conditions in a nitrogen atmosphere. Chloromethyl methyl ether (27.6 g, 343 mmol) was added dropwise. After the dropwise addition, [MB2-3] was synthesized by reacting for 2 hours under ice-cooling conditions.
4-dimethylaminopyridine (0.966 g, 7.90 mmol) was added to the above reaction solution, and methacryloyl chloride (33.0 g, 316 mmol) was added dropwise under ice-cooling conditions in a nitrogen atmosphere. After the dropwise addition, the mixture was reacted at room temperature for 20 hours to eliminate the raw materials. After the reaction was completed, the reaction solution was diluted with ethyl acetate (1230 g), and the organic phase was washed three times with pure water. Subsequently, after dehydrating the organic phase with sodium sulfate, 2,6-di-tert-butyl-p-cresol (291 mg, 1.32 mmol) was added to the organic phase and concentrated under reduced pressure to obtain [MB2-4]. I got some rough stuff.
Ethanol (EtOH, 410 g) and pyridinium p-toluenesulfonate (13.2 g, 52.7 mmol) were added to the obtained crude [MB2-4], and the mixture was reacted at 70° C. for 19 hours. After the reaction was completed, the reaction solution was poured into pure water (1500 g) to precipitate crude crystals, and the crude crystals were collected by filtration. Subsequently, recrystallization was performed with ethyl acetate (450 g) and MeCN (200 g), and the crystals were filtered and dried under reduced pressure to obtain 64.6 g (white crystals) of [MB2-5] (yield: 63 %).

<Synthesis of [MB2-6]>
In a 1,000 mL four-necked flask, add THF (213 g), [MB2-5] (35.5 g, 106 mmol), tert-butyl 4-hydroxybenzoate (22.1 g, 114 mmol), and 4-dimethylaminopyridine ( 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC/HCl, 24.3 g, 127 mmol) was added under nitrogen atmosphere at room temperature for 23 hours. The raw materials were eliminated by the reaction. After the reaction was completed, the reaction solution was diluted with ethyl acetate (530 g), and the organic phase was washed three times with pure water. After collecting the organic phase, it was concentrated under reduced pressure to obtain a crude product. The obtained crude product was diluted with 2-propanol (76 g) and hexane (70 g), cooled to -20°C to precipitate crystals, filtered, and dried under reduced pressure to obtain [MB2-6] at 43% .9g was obtained (yield: 81%).

<Synthesis of [MB2]>
Formic acid (307 g) and [MB2-6] (43.9 g, 85.6 mmol) were placed in a 1,000 mL four-neck flask and reacted at 50° C. for 1 hour to eliminate the raw materials. After the reaction was completed, the reaction solution was poured into pure water (880 g) to precipitate crystals, and the crude product was collected by filtration. The crude material was dissolved in THF (132 g), concentrated under reduced pressure to a solution weight of 44 g, slurry washed by adding MeCN (66 g), and the filtered material was dried under reduced pressure to obtain 22.4 g of [MB2] (white crystals). (yield: 57%). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target MB2.
¹ H-NMR (400 MHz, [D ₆ ]-DMSO): δ (ppm) = 13.1 (s, 1H), 8.02-8.06 (m, 2H), 7.76-7.79 ( m, 1H), 7.59 (d, 1H), 7.39-7.42 (m, 2H), 7.16 (d, 1H), 6.02 (s, 1H), 5.67 (s , 1H), 4.07-4.12 (m, 4H), 3.85 (s, 3H), 1.88 (s, 3H), 1.74-1.79 (m, 2H), 1. 62-1.69 (m, 2H), 1.38-1.48 (m, 4H)

<<Synthesis of MB4>>

MC1 (10.0 g, 32.6 mmol), DMF (50 mg) and THF (50 g) were added to a 200 mL four-necked flask, and oxalyl chloride (4.56 g, 35.9 mmol) was added dropwise, followed by stirring at room temperature. After the reaction was completed, the reaction solution was concentrated using a rotary evaporator to obtain a chlorinated product (pale yellow liquid). THF (50 g) and methoxymethyl 3-(4-hydroxyphenyl)propionate (7.19 g, 34.2 mmol) were added to the obtained chlorinated product, cooled on ice under a nitrogen atmosphere, and triethylamine (3.96 g, 39 mmol) was added to the obtained chlorinated product. .1 mmol) was added dropwise and stirred at room temperature. After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. Ethyl acetate (100 g) was added, and extraction was performed using pure water (200 g). The organic layer was concentrated using a rotary evaporator and the solvent was distilled off to obtain MB4-1 (light brown liquid). The obtained MB4-1, MeCN (150 g), and 1N hydrochloric acid (50 g) were added to a 500 mL one-neck flask and stirred at room temperature. After the reaction was completed, the reaction solution was poured into pure water (200 g), and the precipitate was filtered off. The obtained crude product was recrystallized from ethanol (50 g) to obtain 11.2 g of MB4 (white solid) (yield: 76%). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target MB4.
¹ H-NMR (400 MHz, [D ₆ ]-DMSO): δ (ppm) = 12.2 (s, 1H), 8.03-8.07 (d, 2H), 7.28-7.32 ( d, 2H), 7.13-7.17 (d, 2H), 7.08-7.12 (d, 2H), 6.02 (s, 1H), 5.66 (s, 1H), 4 .06-4.13 (m, 4H), 2.82-2.88 (m, 2H), 2.54-2.59 (t, 2H), 1.88 (s, 3H), 1.72 -1.80 (m, 2H), 1.61-1.69 (m, 2H), 1.38-1.50 (m, 4H).

<<Synthesis of MB5>>

In a 200 mL four-neck flask, MB1 (15.0 g, 35.2 mmol), methoxymethyl 3-(4-hydroxyphenyl)propionate (7.78 g, 37.0 mmol), THF (75 g), 1-(3- Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (8.09 g, 42.2 mmol) and 4-dimethylaminopyridine (0.43 g, 3.52 mmol) were added and stirred at room temperature. After the reaction was completed, MB5-1 (white solid) was obtained by pouring into pure water (450 g) and filtering off the precipitate. The obtained MB5-1, MeCN (225 g), and 1N hydrochloric acid (75 g) were added to a 500 mL one-neck flask and stirred at room temperature. After the reaction was completed, the deposited precipitate was filtered off and repulped and washed with MeCN (45 g). The obtained crude product was recrystallized from a mixed solvent of THF (150 g) and MeCN (150 g) to obtain 12.7 g of MB5 (white solid) (yield: 63%). The results of ¹ H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target MB5.
¹ H-NMR (400 MHz, [D ₆ ]-DMSO): δ (ppm) = 12.2 (s, 1H), 8.20-8.24 (d, 2H), 8.08-8.12 ( d, 2H), 7.50-7.54 (d, 2H), 7.31-7.35 (d, 2H), 7.19-7.23 (d, 2H), 7.11-7. 16 (d, 2H), 6.02 (s, 1H), 5.67 (s, 1H), 4.08-4.14 (m, 4H), 2.84-2.89 (t, 2H) , 2.54-2.60 (t, 2H), 1.88 (s, 3H), 1.73-1.81 (m, 2H), 1.62-1.69 (m, 2H), 1 .38-1.51 (m, 4H).

[1] Synthesis of polymer <Synthesis Example 1>
MA1 (3.99 g, 12.0 mmol), MC1 (4.90 g, 16.0 mmol), MB1 (5.12 g, 12.0 mmol) and AIBN (0.66 g, 4.0 mmol) in NMP (20.5 g). 00 mmol) to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.7 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain a polymer solution P-1.

<Synthesis example 2>
In NMP (24.3 g) were MA1 (3.69 g, 11.1 mmol), MC1 (1.13 g, 3.70 mmol), MB1 (9.47 g, 22.2 mmol) and AIBN (0.61 g, 3. 70 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (10.4 g) at 60° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was reacted at 60° C. for 12 hours to obtain a polymer solution P-2.

<Synthesis example 3>
MA1 (3.59 g, 10.8 mmol), MB1 (10.8 g, 25.2 mmol) and AIBN (0.59 g, 3.60 mmol) were dissolved in NMP (24.4 g) to prepare a monomer mixed solution. did. The monomer mixed solution was added dropwise to NMP (10.4 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60°C for 12 hours to obtain a polymer solution P-3.

<Synthesis example 4>
In NMP (24.3 g) were MA1 (3.59 g, 10.8 mmol), MB1 (9.98 g, 23.4 mmol), MC2 (0.69 g, 1.80 mmol) and AIBN (0.59 g, 3. 60 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (10.4 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60°C for 12 hours to obtain a polymer solution P-4.

<Synthesis example 5>
In NMP (20.0 g), MA1 (3.69 g, 11.1 mmol), MC1 (2.27 g, 7.40 mmol), MB1 (6.31 g, 14.8 mmol), MC2 (1.42 g, 3. 70 mmol) and AIBN (0.61 g, 3.70 mmol) were dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.3 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60°C for 12 hours to obtain a polymer solution P-5.

<Synthesis example 6>
In NMP (20.8 g), MA1 (3.89 g, 11.7 mmol), MC1 (2.39 g, 7.80 mmol), MB1 (4.99 g, 11.7 mmol), MC2 (2.98 g, 7. 80 mmol) and AIBN (0.64 g, 3.90 mmol) were dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.9 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-6.

<Synthesis example 7>
In NMP (20.6 g) were MA1 (2.09 g, 6.30 mmol), MC1 (8.36 g, 27.3 mmol), MB1 (3.58 g, 8.40 mmol) and AIBN (0.69 g, 4. 20 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.7 g) over 2 hours at 60° C. under a nitrogen atmosphere. After completion of the dropwise addition, reaction was carried out at 60°C for 12 hours to obtain polymer solution P-7.

<Synthesis example 8>
In NMP (20.5 g) were MA1 (1.94 g, 5.85 mmol), MC1 (5.38 g, 17.6 mmol), MB1 (6.65 g, 15.6 mmol) and AIBN (0.64 g, 3. 90 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.6 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain a polymer solution P-8.

<Synthesis example 9>
In NMP (24.1 g) were MA1 (1.84 g, 5.55 mmol), MC1 (2.83 g, 9.25 mmol), MB1 (9.47 g, 22.2 mmol) and AIBN (0.61 g, 3. 70 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (10.3 g) at 60° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, reaction was carried out at 60°C for 12 hours to obtain polymer solution P-9.

<Synthesis example 10>
In NMP (20.6 g), MA1 (1.94 g, 5.85 mmol), MC1 (5.38 g, 17.6 mmol), MB1 (4.99 g, 11.7 mmol), MB2 (1.78 g, 3. 90 mmol) and AIBN (0.64 g, 3.90 mmol) were dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.7 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-10.

<Synthesis example 11>
In NMP (21.0 g) were MA1 (2.09 g, 6.30 mmol), MC1 (8.36 g, 27.3 mmol), MB2 (3.83 g, 8.40 mmol) and AIBN (0.69 g, 4. 20 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.0 g) at 60° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-11.

<Synthesis example 12>
In NMP (20.9 g), MA1 (1.99 g, 6.00 mmol), MC1 (5.51 g, 18.0 mmol), MB1 (5.12 g, 12.0 mmol), MC3 (1.65 g, 4. 00 mmol) and AIBN (0.66 g, 4.00 mmol) were dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.9 g) at 60° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-12.

<Synthesis example 13>
In NMP (20.9 g) were MA1 (2.09 g, 6.30 mmol), MC1 (8.36 g, 27.3 mmol), MB3 (3.80 g, 8.40 mmol) and AIBN (0.69 g, 4. 20 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.0 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-13.

<Synthesis example 14>
In NMP (21.1 g) were MA1 (1.94 g, 5.85 mmol), MC1 (5.38 g, 17.6 mmol), MB4 (7.09 g, 15.6 mmol) and AIBN (0.64 g, 3. 90 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.0 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-14.

<Synthesis example 15>
MA1 (1.99 g, 6.00 mmol), MC1 (7.97 g, 26.0 mmol), MB5 (4.58 g, 8.00 mmol) and AIBN (0.66 g, 4.0 mmol) in NMP (21.3 g). 00 mmol) to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.2 g) at 60° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-15.

<Synthesis example 16>
In NMP (21.1 g) were MA1 (2.04 g, 6.15 mmol), MC1 (6.91 g, 22.6 mmol), MB6 (5.41 g, 12.3 mmol) and AIBN (0.67 g, 4. 10 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.0 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the mixture was reacted at 60° C. for 12 hours to obtain polymer solution P-16.

<Synthesis example 17>
MA1 (2.24 g, 6.75 mmol), MC1 (11.7 g, 38.3 mmol) and AIBN (0.74 g, 4.50 mmol) were dissolved in NMP (20.6 g) to prepare a monomer mixed solution. did. The monomer mixed solution was added dropwise to NMP (13.7 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the mixture was reacted at 60° C. for 12 hours to obtain polymer solution P-17.

<Synthesis example 18>
In NMP (20.8 g) were MA1 (4.39 g, 13.2 mmol), MC1 (8.09 g, 26.4 mmol), MC2 (1.68 g, 4.40 mmol) and AIBN (0.72 g, 4. 40 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (13.9 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours to obtain polymer solution P-18.

<Synthesis example 19>
In NMP (21.3 g) were MA1 (4.19 g, 12.6 mmol), MC1 (5.15 g, 16.8 mmol), MC3 (5.20 g, 12.6 mmol) and AIBN (0.69 g, 4. 20 mmol) was dissolved to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to NMP (14.2 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the addition was completed, the mixture was reacted at 60° C. for 12 hours to obtain a polymer solution P-19.

<Synthesis example 20>
MD1 (17.5 g, 39.9 mmol) and AIBN (0.328 g, 2.00 mmol) were dissolved in THF (50.0 g) to prepare a monomer mixed solution. The monomer mixed solution was added dropwise to THF (21.4 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was added to a mixed solution of methanol (450 g) and pure water (180 g) to reprecipitate the polymer. Subsequently, polymer powder P-20 was obtained by filtration, washing with methanol, and drying.

Table 1 shows the monomer compositions of the polymer solutions P-1 to P-19 and polymer powder P-20 obtained above. In Table 1, the numbers in parentheses for the composition represent the blending amount (mol parts) of each monomer based on the total of 100 mole parts of the monomers used.

[2] Preparation of retardation film forming material <Preparation Example 1>
By adding NMP (0.4 g), BCS (3.6 g) and R40 (3.0 mg) to the polymer solution P-1 (20 g) obtained in Synthesis Example 1 and stirring, polymer solution T-1 was prepared. I got it. This polymer solution T-1 was directly used as a material for forming a retardation film.

<Preparation Examples 2 to 19>
Polymer solutions T-2 to T-19 were obtained by carrying out the same procedure as in Preparation Example 1 except that the polymer solution used was replaced with P-2 to P-19 from P-1. These polymer solutions T-2 to T-19 were used as materials for forming a retardation film as they were.

<Preparation example 20>
By adding CPN (11.3 g), BCS (3.75 g) and R40 (2.0 mg) to the polymer powder P-20 (3.75 g) obtained in Synthesis Example 20 and stirring, a polymer solution was prepared. Obtained T-20. This polymer solution T-20 was directly used as a material for forming a retardation film.

<Preparation example 21>
Polymer solution P-8 (20 g) obtained in Synthesis Example 8 was poured into a methanol/pure water mixed solvent to precipitate the polymer, filtered, and washed with methanol to obtain polymer powder P-8 (4.5 g). I got it. NMP (2.0 g), PGME (3.5 g), BCS (1.0 g), PGMEA (1.7 g), and F563 (9.0 mg) were added to the obtained polymer powder P-8 (1.8 g). ) was added and stirred to obtain polymer solution T-21. This polymer solution T-21 was directly used as a material for forming a retardation film.

[3] Production of single-layer retardation film <Example 1>
Polymer solution T-1 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (900 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 170° C. for 20 minutes to produce a glass substrate S-1 with a retardation film.

<Example 2>
Polymer solution T-2 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (600 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 190° C. for 20 minutes to produce a glass substrate S-2 with a retardation film.

<Example 3>
Polymer solution T-3 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.5 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (400 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 200° C. for 20 minutes to produce a glass substrate S-3 with a retardation film.

<Example 4>
Polymer solution T-4 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.5 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (800 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 200° C. for 20 minutes to produce a glass substrate S-4 with a retardation film.

<Example 5>
Polymer solution T-5 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (400 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 190° C. for 20 minutes to produce a glass substrate S-5 with a retardation film.

<Example 6>
Polymer solution T-6 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (600 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 190° C. for 20 minutes to produce a glass substrate S-6 with a retardation film.

<Example 7>
Polymer solution T-7 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.5 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (800 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 170° C. for 20 minutes to produce a glass substrate S-7 with a retardation film.

<Example 8>
Polymer solution T-8 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 2.0 μm. This substrate was dried on a hot plate at 60° C. for 4 minutes, and then ultraviolet light (1,000 mJ/cm ² ) with a wavelength of 365 nm was applied to the substrate from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. was irradiated. It was heated in an IR oven at 190° C. for 20 minutes to produce a glass substrate S-8 with a retardation film.

<Example 9>
Polymer solution T-9 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.5 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (800 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 170° C. for 20 minutes to produce a glass substrate S-9 with a retardation film.

<Example 10>
Polymer solution T-10 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (400 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 180° C. for 20 minutes to produce a glass substrate S-10 with a retardation film.

<Example 11>
Polymer solution T-11 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 4.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (200 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 140° C. for 20 minutes to produce a glass substrate S-11 with a retardation film.

<Example 12>
Polymer solution T-12 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (200 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 160° C. for 20 minutes to produce a glass substrate S-12 with a retardation film.

<Example 13>
Polymer solution T-13 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 2.5 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (400 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 160° C. for 20 minutes to produce a glass substrate S-13 with a retardation film.

<Example 14>
Polymer solution T-14 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.2 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (100 mJ/cm ² ) with a wavelength of 365 nm were irradiated onto this substrate from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 140° C. for 20 minutes to produce a glass substrate S-14 with a retardation film.

<Example 15>
Polymer solution T-15 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.2 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (200 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 170° C. for 20 minutes to produce a glass substrate S-15 with a retardation film.

<Example 16>
Polymer solution T-16 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 2.3 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (800 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 120° C. for 20 minutes to produce a glass substrate S-16 with a retardation film.

<Example 17>
Polymer solution T-21 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a bar coater to a film thickness of about 2.5 μm. This substrate was dried in a thermal circulation oven at 80°C for 4.5 minutes, and then ultraviolet light (1,000 mJ/cm) with a wavelength of 365 nm was applied to the substrate from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. ² ) was irradiated. It was heated in an IR oven at 190° C. for 20 minutes to produce a glass substrate S-17 with a retardation film.

<Comparative example 1>
Polymer solution T-17 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a 60°C hot plate for 4 minutes, and then ultraviolet rays (800 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 140° C. for 20 minutes to produce a glass substrate R-1 with a retardation film.

<Comparative example 2>
Polymer solution T-18 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (200 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 160° C. for 20 minutes to produce a glass substrate R-2 with a retardation film.

<Comparative example 3>
Polymer solution T-19 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 3.0 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet rays (50 mJ/cm ² ) with a wavelength of 365 nm were irradiated from a high-pressure mercury lamp through a cut filter (365 nm bandpass filter) and a polarizing plate. did. It was heated in an IR oven at 110° C. for 20 minutes to produce a glass substrate R-3 with a retardation film.

<Comparative example 4>
Polymer solution T-20 was filtered through a filter with a pore size of 5.0 μm, and then coated onto an alkali-free glass substrate using a spin coater to a film thickness of about 0.8 μm. This substrate was dried on a hot plate at 60°C for 4 minutes, and then ultraviolet light (600 mJ/cm ² ) with a wavelength of 365 nm was applied to this substrate from a high-pressure mercury lamp through a cut filter (325 nm long wave pass filter) and a polarizing plate. Irradiated. It was heated for 20 minutes in a thermal circulation oven at 130° C. to produce a glass substrate R-4 with a retardation film.

The retardation value and NZ coefficient of the substrates S-1 to S-17 and R-1 to R-4 with each retardation film were evaluated by the following method.

[Phase difference value evaluation]
The linear phase difference at a wavelength of 550 nm was evaluated using AxoScan manufactured by Axometrics, and the results are summarized in Table 2.

[NZ coefficient evaluation]
The refractive index of the retardation film in the three-dimensional direction at a wavelength of 550 nm was measured using AxoScan manufactured by Axometrics, and the NZ coefficient was calculated. The NZ coefficient is an index of the magnitude relationship of three-dimensional refractive index, and is expressed by the following formula.
NZ coefficient = (nx-nz)/(nx-ny)
nx: refractive index in the x-axis direction (slow axis direction) ny: refractive index in the y-axis direction (direction orthogonal to the slow axis) nz: refractive index in the z-axis direction (thickness direction) Glass substrate S with a retardation film For -1 to S-17 and R-1 to R-3, it is assumed that the average refractive index of the retardation film is 1.55, and for the glass substrate R-4 with the retardation film, the average refractive index is 1.60. Table 2 summarizes the results of calculating the NZ coefficient based on this assumption.

Retardation films R-1 to R-4 that do not contain terminal carboxylic acid side chains, which have two or more ring structures and have a structure in which the two rings on the terminal side are single bonds and are not covalently bonded. The NZ coefficient was close to 0 or 1. On the other hand, the retardation films S-1 to S-17 manufactured with the compositions having the above side chains had NZ coefficients of 0.4 to 0.6.

Claims

(A) A terminal having a side chain of a terminal carboxylic acid having a photoreactive site and two or more aromatic ring structures, and a structure in which the two rings on the terminal side are single bonds and are not covalently bonded. A composition for a retardation film comprising a side chain type copolymer containing a carboxylic acid side chain, and (B) an organic solvent.
The above (A) side chain type copolymer is a side chain type copolymer having a side chain having a photoreactive site represented by the following formula (a) and a side chain having a side chain having a site represented by the following formula (b). The composition for a retardation film according to claim 1, which is a combination.

(In the formula, R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. -CH 2 CH 2 - may be substituted with -CH=CH-, and -CH 2 - in R 1 may be substituted with -O-, -NH-C(=O)-, -C(= O) -NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- may be substituted with a group selected from the group consisting of: However, adjacent --CH 2 -- groups are not substituted with these groups at the same time.
R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group.
R 3 is a single bond, -CH 2 -, -O-, -C(=O)-O-, -OC(=O)- or -CH=CH-C(=O)-O- be.
R 4 is a divalent aromatic group, -Ph-Cy-, -Cy-Ph-, or a divalent fused cyclic group (where Ph represents a phenylene group and Cy represents a cyclohexanediyl group). be.
R 5 is -CH 2 -, -O-, -NH-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CH=CH- C(=O)-O-, -C(=O)-NH-, -NH-C(=O)- or -NH-C(=O)-NH-.
R 6 is an alkylene group having 1 to 10 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Furthermore, -CH 2 - in R 6 may be substituted with a group selected from the group consisting of -O-, -NH- and -C(=O)-. Adjacent --CH 2 -- groups may be substituted with these groups at the same time.
The hydrogen atom in the ring structure and CH═CH structure in formula (a) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a halogen group, a cyano group, and a nitro group.
The hydrogen atom in the ring structure in formula (b) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms. , a halogen group, a cyano group, and a nitro group.
When two or more R 2 , R 3 , R 4 or R 5 are present, the plurality of R 2 , R 3 , R 4 or R 5 may be the same or different.
a is 0, 1 or 2.
b is 0 or 1.
c is an integer satisfying 0≦c≦2b+4.
d is 1 or 2.
e is 0 or 1.
f is 0 or 1.
The broken lines are bonds. )
The composition for a retardation film according to claim 2, wherein the side chain having a photoreactive site represented by the above formula (a) is represented by the following formula (a1).

(In the formula, R 1 , R 2 and a are the same as above.
R 3A is a single bond, -O-, -C(=O)-O- or -OC(=O)-. When two or more R 3As exist, the plural R 3As may be the same or different.
The hydrogen atom in the benzene ring and in the CH═CH structure in formula (a1) is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. -6 may be substituted with a substituent selected from a haloalkoxy group, a halogen group, a cyano group, and a nitro group.
The broken lines are bonds. )
The polymer composition and composition for a retardation film according to claim 2, wherein the number of ring structures in the side chain represented by the above formula (b) is 3 or less.
The composition for a retardation film according to claim 1, wherein the side chain type polymer exhibits liquid crystallinity.
(I) a step of applying the composition for a retardation film according to any one of claims 1 to 5 on a substrate to form a coating film;
(II) A method for producing a single-layer retardation material, comprising the steps of: (II) irradiating the coating film with polarized ultraviolet rays; and (III) heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.
A single-layer retardation material obtained from the composition according to any one of claims 1 to 5.