KR20230124993A - Method for manufacturing single-layer retardation film and polymer composition for forming single-layer retardation film - Google Patents

Abstract

(I) a step of applying a polymer composition for forming a single-layer retardation film comprising a polymer having a photoreactive site that reacts with ultraviolet rays in a side chain on a substrate and drying it to form a coating film; (II) to the coating film, 1st exposure step of irradiating 1 polarization ultraviolet-ray, and (III) the 2nd polarization|polarization-axis direction different from the 1st polarization ultraviolet-ray on the same surface as the surface irradiated with the 1st polarization ultraviolet-ray to the coating film irradiated with the said polarization ultraviolet-ray A method for manufacturing a single layer retardation film including a second exposure step of irradiating ultraviolet rays is provided.

Description

Method for manufacturing single-layer retardation film and polymer composition for forming single-layer retardation film

The present invention relates to a method for producing a single-layer retardation film and a polymer composition for forming a single-layer retardation film.

For display devices such as liquid crystal display devices and organic electroluminescence (EL) display devices, it is known to use a circular polarizing plate in order to suppress reflection of external light on the display surface due to demands such as improvement of display quality. .

It is known that such a circular polarizing plate is a combination of a retardation plate and a polarizer. Retardation plates include a quarter-wave plate that converts linearly polarized light into circularly polarized light, and a half-wavelength plate that converts the plane of polarization vibration of linearly polarized light by 90°. These retardation plates are capable of accurately converting a specific monochromatic light into a retardation of 1/4 wavelength or 1/2 wavelength of the light ray wavelength.

However, conventional retardation plates have a problem that polarized light output through the retardation plate is converted into colored polarized light. This is because the retardation plate has positive-wavelength dispersion in which the phase difference decreases with each increase in wavelength, and a distribution occurs in the polarization state for each wavelength for white light, which is a synthesized wave in which light rays in the visible region are mixed. This is because it is impossible to precisely adjust to the phase difference of 1/4 wavelength.

In order to solve this problem, a broadband retardation plate capable of imparting a uniform retardation to light in a wide wavelength range, a so-called retardation plate having reverse wavelength dispersion, has been studied (for example, Patent Documents 1 to 6). .

A retardation plate having reverse wavelength dispersion is produced mainly by applying a polymerizable composition containing a special low-molecular polymerizable compound to a film substrate. Therefore, many developments of low molecular polymerizable liquid crystal compounds having reverse wavelength dispersion or polymerizable compositions using the same have been conducted. However, since these low-molecular polymerizable liquid crystal compounds or polymerizable compositions are synthesized in multiple steps by utilizing a synthesis method using very expensive reagents, they have a problem in terms of cost.

Japanese Unexamined Patent Publication No. 10-68816 Japanese Unexamined Patent Publication No. 2002-267838 Japanese Unexamined Patent Publication No. 2005-289980 Japanese Unexamined Patent Publication No. 2007-86105 Japanese Unexamined Patent Publication No. 2011-42606 Japanese Unexamined Patent Publication No. 2013-164501

The present invention has been made in view of the above problems, and a manufacturing method enabling the production of a single layer retardation film exhibiting flat or reverse wavelength dispersion at low cost without using a low molecular weight polymerizable liquid crystal compound having reverse wavelength dispersion, and a manufacturing method thereof It is an object of the present invention to provide a polymer composition for forming a single-layer retardation film used for

The inventors of the present invention, as a result of repeating various studies to solve the above problems, in producing a single-layer retardation film having flat or reverse wavelength dispersion using a composition containing a polymer having positive wavelength dispersion, the polymer As a method, using a polymer having a photoreactive site that photoreacts with ultraviolet rays (photodimerization, photoisomerization, or photofries dislocation), performing a process of irradiating polarized ultraviolet rays from the same surface twice or more, and second exposure found that by using a polarized ultraviolet ray different from the polarization axis direction of the polarized ultraviolet ray in the first exposure, the original retardation is expressed, and the forward wavelength dispersion is suppressed to obtain a single layer retardation film showing reverse wavelength dispersion, completed the present invention.

That is, the present invention provides a method for producing the following single-layer retardation film and a polymer composition for forming a single-layer retardation film.

1. (I) a step of applying a polymer composition for forming a single-layer retardation film comprising a polymer having a photoreactive site that photoreacts with ultraviolet rays on a side chain on a substrate and drying it to form a coating film;

(II) a first exposure step of irradiating the coating film with first polarized ultraviolet rays; and

(III) a single layer including a second exposure step of irradiating a second polarized ultraviolet ray having a different polarization axis direction from the first polarized ultraviolet ray on the same surface as the surface irradiated with the first polarized ultraviolet ray to the coating film irradiated with the polarized ultraviolet ray; A method for manufacturing a phase contrast film.

2. Further, (IV) Method of producing a single-layer phase contrast film in 1, including a step of heating the coating film obtained in step (III).

3. Steps (II) and (III) WHEREIN: 1 or 2 methods of producing a single-layer phase contrast film in which polarized ultraviolet rays are irradiated from the interface side of the coating film and air.

4. The method for producing a single-layer retardation film according to any one of 1 to 3, wherein the side chain having a photoreactive site that photoreacts with the ultraviolet rays is represented by any one of the following formulas (a1) to (a6).

[Formula 1]

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.

L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also is a single bond

Y ¹ and Y ² are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and the naphthylene group are cyano groups, halogen atoms, alkyl groups of 1 to 5 carbon atoms, or alkyl groups of 2 to 6 carbon atoms It may be substituted with a carbonyl group or an alkoxy group having 1 to 5 carbon atoms.

P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms in the phenylene group are cyano groups, halogen atoms, It may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. When the number of Q ¹ is 2, each Q ¹ may be the same or different, and when the number of Q ² is 2, each Q ² may be the same or different.

R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.

X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2, each X ¹ may be the same or different, and when the number of X ² is 2, each X ² may be the same or different.

Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded thereto are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom , a C1-C5 alkyl group or a C1-C5 alkoxy group.

E is -C(=O)-O-, -O-C(=O)-, -C(=O)-S- or -S-C(=O)-.

G ¹ and G ² are each independently N or CH.

The dashed line is the bond hand.)

5. The manufacturing method of the monolayer retardation film in any one of 1-4 in which the said polymer has a side chain which neither photodimerization nor photoisomerization further.

6. The manufacturing method of the monolayer retardation film of 5 which is that the said side chain which neither photodimerization nor photoisomerization is further represented by any of following formula (b1) - (b11).

[Formula 2]

[Formula 3]

(In the formula, A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, or -NH-C(=O)-.

R ¹ is -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 group of 5 to 8 carbon atoms, or 1 to 12 carbon atoms It is an alkyl group of or a C1-C12 alkoxy group.

R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, and some or all of the hydrogen atoms in these groups are -NO ₂ , -CN, a halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.

R ³ 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 group of 5 to 8 carbon atoms, or a carbon number It is an alkyl group of 1-12 or an alkyloxy group of 1-12 carbon atoms.

E is -C(=O)-O-, -O-C(=O)-, -C(=O)-S- or -S-C(=O)-.

a is an integer of 1 to 12;

k1-k5 are each independently an integer of 0-2, but the sum of k1-k5 is 2 or more.

Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.

m1, m2 and m3 are each independently an integer of 1-3.

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 line is a bonding hand.

In addition, some or all of the hydrogen atoms of the benzene ring and naphthalene ring in the formula may be substituted with a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. .)

7. A polymer composition for forming a single-layer retardation film comprising a polymer having a photoreactive site that photoreacts with ultraviolet rays in a side chain,

(I) a step of applying the composition on a substrate and drying it to form a coating film, (II) a first exposure step of irradiating the coating film with first polarized ultraviolet rays, and (III) a coating film irradiated with the polarized ultraviolet rays , Further, by a second exposure step of irradiating second polarized ultraviolet light having a different polarization axis direction from the first polarized ultraviolet light on the same surface as the surface irradiated with the first polarized ultraviolet light, the wavelength dispersion exhibits flat dispersion or reverse wavelength dispersion. A polymer composition for forming a single-layer retardation film for providing a single-layer retardation film.

8. The polymer composition for forming a single-layer retardation film according to 7, wherein the side chain having a photoreactive site that photoreacts with ultraviolet rays is represented by any one of the following formulas (a1) to (a6).

[Formula 4]

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.

L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also is a single bond

Y ¹ and Y ² are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and the naphthylene group are cyano groups, halogen atoms, alkyl groups of 1 to 5 carbon atoms, or alkyl groups of 2 to 6 carbon atoms It may be substituted with a carbonyl group or an alkoxy group having 1 to 5 carbon atoms.

P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms in the phenylene group are cyano groups, halogen atoms, It may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. When the number of Q ¹ is 2, each Q ¹ may be the same or different, and when the number of Q ² is 2, each Q ² may be the same or different.

R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.

X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2, each X ¹ may be the same or different, and when the number of X ² is 2, each X ² may be the same or different.

Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded thereto are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom , a C1-C5 alkyl group or a C1-C5 alkoxy group.

E is -C(=O)-O-, -O-C(=O)-, -C(=O)-S- or -S-C(=O)-.

G ¹ and G ² are each independently N or CH.

The dashed line is the bond hand.)

9. The polymer composition for forming a single-layer retardation film in 8, wherein the polymer has a side chain that neither undergoes photodimerization nor photoisomerization.

10. The polymer composition for forming a single layer retardation film in item 9, wherein the side chain that neither photodimerization nor photoisomerization is represented by any of the following formulas (b1) to (b11).

[Formula 5]

[Formula 6]

(In the formula, A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, or -NH-C(=O)-.

R ¹ is -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 group of 5 to 8 carbon atoms, or 1 to 12 carbon atoms It is an alkyl group of or a C1-C12 alkoxy group.

R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, and some or all of the hydrogen atoms in these groups are -NO ₂ , -CN, a halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.

R ³ 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 group of 5 to 8 carbon atoms, or a carbon number It is an alkyl group of 1-12 or an alkyloxy group of 1-12 carbon atoms.

E is -C(=O)-O-, -O-C(=O)-, -C(=O)-S- or -S-C(=O)-.

a is an integer of 1 to 12;

k1-k5 are each independently an integer of 0-2, but the sum of k1-k5 is 2 or more.

Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.

m1, m2 and m3 are each independently an integer of 1-3.

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 line is a bonding hand.

In addition, some or all of the hydrogen atoms of the benzene ring and naphthalene ring in the formula may be substituted with a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. .)

According to the production method of the present invention, a single-layer retardation film exhibiting flat or reverse wavelength dispersion can be produced conveniently and at low cost using a composition containing a polymer having positive wavelength dispersion. With the single-layer retardation film, linearly polarized light can be converted into circularly polarized light in a broadband.

1 is a graph showing the relationship between linear retardation (Linear Re) and wavelength of a substrate with a retardation film obtained in Example 7;

The manufacturing method of the single-layer retardation film of the present invention,

(I) a step of applying a polymer composition for forming a single-layer retardation film on a substrate and drying it to form a coating film;

(II) a first exposure step of irradiating the coating film with first polarized ultraviolet rays; and

(III) a second exposure step of irradiating a second polarized ultraviolet light having a different polarization axis direction from that of the first polarized ultraviolet ray on the same surface as the surface irradiated with the first polarized ultraviolet ray to the coating film irradiated with the polarized ultraviolet ray; to be characterized In the present invention, the direction of the polarization axis has the same meaning as the direction of vibration of the polarized ultraviolet rays.

[Process (I)]

Step (I) is a step of applying the polymer composition for forming a single-layer retardation film onto a substrate and drying it to form a coating film. More specifically, the polymer composition is applied to a substrate (e.g., a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, On an ITO substrate, a transparent film (a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, a resin film such as an acrylic film)), bar coat, spin coat, flow coat, roll coat, slit coat, It is applied by a method such as spin coating followed by slit coating, an inkjet method, or a printing method. After application, the coating film can be obtained by air drying or by heating with a heating means such as a hot plate, heat circulation type oven, or IR (infrared ray) type oven to evaporate the solvent. When heating with a heating means, the temperature is not particularly limited, but is preferably 30 to 200°C and more preferably 30 to 150°C.

[Polymer composition for forming single-layer phase contrast film]

The polymer composition for forming a single-layer retardation film of the present invention includes a polymer having a photoreactive site that photoreacts with ultraviolet rays in a side chain, specifically, a photosensitive side chain type polymer or liquid crystal capable of expressing liquid crystallinity. A mixed side chain polymer (hereinafter, simply referred to as a side chain polymer) having a sexual side chain polymer and a photosensitive side chain polymer separately is included. The coating film obtained from the said composition is also a film|membrane which has a side chain type polymer containing liquid crystalline property and photosensitivity. The coating film is not subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. And after polarized light irradiation, the side chain type polymer film is subjected to a step of heating to obtain a film (single-layer retardation film) imparted with optical anisotropy. At this time, the minute anisotropy expressed by polarized light irradiation becomes a driving force, and the side chain polymer itself is efficiently reorientated by self-organization. As a result, highly efficient alignment treatment can be realized as a single-layer retardation film, and a single-layer retardation film imparted with high optical anisotropy can be obtained.

Photoreactivity in this invention is any reaction of (A-1) photocrosslinking (photodimerization) reaction, (A-2) photoisomerization, or (A-3) optical fleece dislocation; or multiple reactions; refers to a property that causes The side chain type polymer preferably has a side chain that causes a photocrosslinking reaction (A-1) or a photoisomerization reaction (A-2).

The side chain type polymer is (i) a polymer that exhibits liquid crystallinity in a predetermined temperature range, and is a polymer having photoreactive side chains. The side chain type polymer (ii) preferably reacts with light in a wavelength range of 200 nm to 400 nm, preferably 240 nm to 400 nm, and exhibits liquid crystallinity in a temperature range of 50 to 300°C. The side chain type polymer preferably has (iii) a photoreactive side chain that reacts to light in a wavelength range of 200 nm to 400 nm, preferably 240 nm to 400 nm, particularly polarized ultraviolet light. Since the said side chain polymer exhibits liquid crystallinity in the temperature range of (iv) 50-300 degreeC, it is preferable to have a mesogenic group.

As described above, the side chain type polymer has a photoreactive side chain having photoreactivity. Although the structure of the side chain is not particularly limited, it has a structure that causes a reaction shown in the above (A-1), (A-2) and/or (A-3), particularly (A-1) photocrosslinking reaction and / or (A-2) What has a structure which causes a photoisomerization reaction is preferable. Moreover, the structure which causes (A-1) photocrosslinking reaction is preferable from the point which can maintain the orientation of a side chain type polymer stably for a long period of time even if the structure after the reaction is exposed to external stress, such as heat. In addition, (A-2) a structure that causes a photoisomerization reaction is preferable in that an orientation treatment at a lower exposure amount is possible compared to photocrosslinking or optical fleece transfer, and the production efficiency at the time of retardation film production can be increased.

As for the structure of the side chain of the said side chain type polymer, the one which has a rigid mesogen component is preferable since orientation of a liquid crystal is stable. Examples of the mesogenic component include a biphenyl group, a terphenyl group, a phenylcyclohexyl group, and a phenylbenzoate group, but are not limited thereto.

As a side chain (henceforth also referred to as side chain a) which has a photoreactive site which photoreacts with the ultraviolet-ray contained in the said polymer, what is represented by any of following formula (a1) - (a6) is preferable. Moreover, as for the number of benzene rings which one side chain a has, from a solubility viewpoint to a solvent, less than 3 are preferable.

[Formula 7]

In formulas (a1) to (a6), n1 and n2 are each independently 0, 1, 2 or 3. L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms. T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms. A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also is a single bond Y ¹ and Y ² are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and the naphthylene group are cyano groups, halogen atoms, alkyl groups of 1 to 5 carbon atoms, or alkylcarbonyl groups of 2 to 6 carbon atoms. Or you may be substituted by the C1-C5 alkoxy group. P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms in the phenylene group are cyano groups, halogen atoms, It may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. When the number of Q ¹ is 2, each Q ¹ may be the same or different, and when the number of Q ² is 2, each Q ² may be the same or different. R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2, each X ¹ may be the same or different, and when the number of X ² is 2, each X ² may be the same or different. Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded thereto are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom , a C1-C5 alkyl group or a C1-C5 alkoxy group. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. G ¹ and G ² are each independently N or CH. The broken line is a bonding hand.

The alkylene group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof 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, A decane-1,10-diyl group etc. are mentioned.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The alkyl group having 1 to 5 carbon atoms may be either linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, An n-pentyl group etc. are mentioned.

Specific examples of the alkylcarbonyl group having 2 to 6 carbon atoms include methylcarbonyl (acetyl) group, ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, and n-pentylcarbonyl group.

A methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group etc. are mentioned as a specific example of the said C1-C5 alkoxy group.

Specific examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group and a cyclooctanediyl group.

A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned as a specific example of the said C3-C7 cycloalkyl group.

As side chain a, it is represented by the following formula (a1-1), (a1-2), (a2-1), (a3-1), (a4-1), (a5-1) or (a6-1) it is more preferable

[Formula 8]

(In the formula, L, A ¹ , A ² , Y ¹ , Y ² , P ¹ , Q ¹ , T ¹ , R, X ¹ , Cou, E, G ¹ , G ² , n1 and the broken line are the same as above. do)

As a side chain represented by a formula (a1-1), a side chain represented by the following formula (a1-1-1) is preferable, and as a side chain represented by a formula (a1-2), a formula (a1-2-1 ) The side chain represented by is preferable.

[Formula 9]

(In the formula, L, R and the broken line are the same as above)

As a side chain represented by formula (a2-1), the side chain represented by the following formula (a2-1-1) is preferable.

[Formula 10]

(In the formula, L, A ² , Q ¹ , T ¹ , R and the broken line are the same as above.)

As a side chain represented by a formula (a3-1), a side chain represented by the following formula (a3-1-1), (a3-1-2) or (a3-1-3) is preferable.

[Formula 11]

(In the formula, L, Cou and broken lines are the same as above)

As a side chain represented by formula (a4-1), the side chain represented by the following formula (a4-1-1), (a4-1-2), (a4-1-3) or (a4-1-4) this is preferable

[Formula 12]

(In the formula, L, R and the broken line are the same as above)

As a side chain represented by a formula (a5-1), a side chain represented by the following formula (a5-1-1) or (a5-1-2) is preferable.

[Formula 13]

(In the formula, L, R and the broken line are the same as above)

As a side chain represented by a formula (a6-1), a side chain represented by the following formula (a6-1-1), (a6-1-2) or (a6-1-3) is preferable.

[Formula 14]

(In the formula, L, R and the broken line are the same as above)

The side chain type polymer used in the present invention has photosensitive side chains bonded to the main chain, and is suitable for optimal light selected from the wavelengths of 200 nm to 400 nm, in particular, to light with wavelengths of 254 nm, 313 nm and 365 nm. It can be sensitized to cause cross-linking reactions, isomerization reactions or fris dislocations. The structure of the photosensitive side chain type polymer is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. When the side chain type polymer is used as a single layer retardation film, stable optical anisotropy can be obtained.

More specific examples of the structure of the photosensitive side chain type polymer include (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and norbornene. A structure having a main chain composed of at least one member selected from the group consisting of radical polymerizable groups such as the like and siloxane, and a side chain a is preferable.

Moreover, the said side chain type polymer may also contain the side chain (henceforth, also referred to as side chain b) which does neither photodimerization nor photoisomerization. As such a side chain b, those represented by any of the following formulas (b1) to (b11) are preferred, but are not limited thereto. In addition, in the following formula, a broken line is a bond.

[Formula 15]

[Formula 16]

In formulas (b1) to (b11), A ³ and A ⁴ each independently represent a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. R ¹ is -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 group of 5 to 8 carbon atoms, or 1 to 12 carbon atoms It is an alkyl group of or a C1-C12 alkoxy group. R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, and some or all of the hydrogen atoms in these groups are -NO ₂ , -CN, a halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. R ³ 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 group of 5 to 8 carbon atoms, or a carbon number It is an alkyl group of 1-12 or an alkyloxy group of 1-12 carbon atoms. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. a is an integer of 1 to 12; k1-k5 are each independently an integer of 0-2, but the sum of k1-k5 is 2 or more. Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more. m1, m2 and m3 are each independently an integer of 1-3. 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 line is a bonding hand. In addition, some or all of the hydrogen atoms of the benzene ring and naphthalene ring in the formula may be substituted with a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. .

Specific examples of the monovalent nitrogen-containing heterocyclic group include a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a pyrrolyl group, and a pyridyl group. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a specific example of the said C5-C8 monovalent alicyclic hydrocarbon group. Moreover, as said alkyl group and an alkoxy group, the thing same as the group illustrated in description of formula (a1) - (a6) is mentioned.

The side chain type polymer used in the present invention can be obtained by polymerizing a monomer giving side chain a and, if necessary, a monomer giving side chain b.

As a monomer giving side chain a (henceforth also referred to as monomer MA), the following formula (M1-1), (M1-2), (M2), (M3), (M4), (M5) or (M6) The compound represented by is mentioned.

[Formula 17]

(In the formula, A ¹ , A ² , D ¹ , L, T 1 , Y ¹ , Y ² , P ¹ , Q ¹ , Q ² , R, Cou, E, X ¹ , X ² , G ¹ , ^{G 2} , n1 and n2 are the same as above)

In the formulas (M1-1), (M1-2), (M2), (M3), (M4), (M5) and (M6), PG is a polymerizable group, and in the following formulas (PG1) to (PG8) The group represented by either is preferable. Among them, an acryl group or a methacryl group represented by formula (PG1) is preferable from the viewpoint of easy control of the polymerization reaction and stability of the polymer.

[Formula 18]

(In the formula, R ^A is a hydrogen atom or a methyl group, and the broken line is a bond with L)

The compound represented by formula (M1-1) is preferably represented by the following formula (M1-1-1), and the compound represented by formula (M1-2) is represented by the following formula (M1-2-1) it is desirable

[Formula 19]

(In the formula, PG, L, Y ¹ , P ¹ and R are the same as above)

As a compound represented by formula (M2), what is represented by the following formula (M2-1) is preferable.

[Formula 20]

(In the formula, PG, A ² , L, T ¹ , Y ¹ , P ¹ , Q ¹ and R are the same as above)

As a compound represented by formula (M3), what is represented by the following formula (M3-1) is preferable.

[Formula 21]

(In the formula, PG, A ¹ , L, X ¹ , Q ¹ , Cou and n1 are the same as above)

As a compound represented by formula (M4), what is represented by the following formula (M4-1) is preferable.

[Formula 22]

(In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , E, R and n1 are the same as above)

As a compound represented by formula (M5), what is represented by the following formula (M5-1) is preferable.

[Formula 23]

(In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , R and n1 are the same as above)

As a compound represented by formula (M6), what is represented by the following formula (M6-1) is preferable.

[Formula 24]

(In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , G ¹ , G ² , R and n1 are the same as above)

As a compound represented by formula (M1-1-1), what is represented by the following formula (M1-1-2) is preferable, and as a compound represented by formula (M1-2-1), the following formula (M1-2- 2) is preferred.

[Formula 25]

(In the formula, PG, L and R are the same as above)

As a compound represented by formula (M2-1), what is represented by the following formula (M2-2) is preferable.

[Formula 26]

(In the formula, PG, A ² , L, T ¹ , Q ¹ and R are the same as above.)

As a compound represented by formula (M3-1), what is represented by the following formula (M3-2), (M3-3) or (M3-4) is preferable.

[Formula 27]

(In the formula, PG, L and Cou are the same as above)

As a compound represented by formula (M4-1), what is represented by the following formula (M4-2), (M4-3), (M4-4) or (M4-5) is preferable.

[Formula 28]

(In the formula, PG, L and R are the same as above)

As a compound represented by formula (M5-1), what is represented by the following formula (M5-2) or (M5-3) is preferable.

[Formula 29]

(In the formula, PG, L and R are the same as above)

As a compound represented by formula (M6-1), what is represented by the following formula (M6-2), (M6-3), or (M6-4) is preferable.

[Formula 30]

(In the formula, PG, L and R are the same as above)

As a compound represented by a formula (M1-1), what is represented by any of the following formula (A-1-1-1) - (A-1-1-13) is mentioned, for example. In the following formulas (A-1-1-1) to (A-1-1-13), PG is a polymerizable group, s1 represents the number of methylene groups, and is an integer of 2 to 9. R ¹¹ is -H, -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ or -CN, and R ¹² is -H, -CH ₃ , -OCH ₃ , -CN or -F.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

As a compound represented by a formula (M1-2), what is represented by any of the following formula (A-1-2-1) - (A-1-2-4) is mentioned, for example. In the following formula, PG is a polymerizable group, and s1 is the same as above.

[Formula 35]

Specific examples of the compound represented by formula (M1-2) include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4- (3-methacryloxypropyl-1-oxy)cinnamic acid, 4-[4-(6-methacryloxyhexyl-1-oxy)benzoyloxy]cinnamic acid, and the like.

As a compound represented by formula (M2), what is represented by either of following formula (A-2-1) - (A-2-9) is mentioned, for example. In the following formulas (A-2-1) to (A-2-9), PG is a polymerizable group, s1 and s2 represent the number of methylene groups, and are each independently an integer of 2 to 9. R ²¹ is -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ , -CN or -F.

[Formula 36]

[Formula 37]

[Formula 38]

As a compound represented by formula (M3), what is represented by either of following formula (A-3-1) - (A-3-5) is mentioned, for example. In the following formula, PG is a polymerizable group, and s1 is the same as above.

[Formula 39]

As a compound represented by formula (M4), what is represented by either of following formula (A-4-1) - (A-4-4) is mentioned, for example. In the following formula, PG is a polymerizable group, and s1 is the same as above.

[Formula 40]

As a compound represented by formula (M5), what is represented by either of following formula (A-5-1) - (A-5-3) is mentioned, for example. In the following formula, PG is a polymerizable group, and s1 is the same as above.

[Formula 41]

As a compound represented by formula (M6), what is represented by either of following formula (A-6-1) - (A-6-3) is mentioned, for example. In the following formula, PG is a polymerizable group, and s1 is the same as above.

[Formula 42]

As for each said monomer, some are commercially available, and some can be manufactured by the method described, for example in International Publication No. 2014/074785.

As an example of the monomer (henceforth also referred to as monomer MB) which gives the side chain b which does neither photodimerization nor photoisomerization, the monomer which can form a mesogenic group in a side chain is mentioned.

The mesogenic group may be a group that forms a mesogen structure alone, such as biphenyl or phenyl benzoate, or a group that becomes a mesogen structure by hydrogen bonding of side chains to each other, such as benzoic acid. As a mesogen group which a side chain has, the following structure is preferable.

[Formula 43]

Specific examples of the monomer MB include radical polymerization of hydrocarbons, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. It is preferable that it is a structure which has a structure which consists of a polymerizable group derived from at least 1 sort(s) selected from the group which consists of a sexual group and a siloxane, and at least 1 sort(s) of formula (b1) - (b11). In particular, monomer MB preferably has a polymerizable group derived from (meth)acrylate.

As a preferable example of monomer MB, what is represented by the following formula (MB-1) - (MB-8) is mentioned. In addition, in the following formula, PG is a polymerizable group, p represents the number of methylene groups, and is an integer of 2-9.

[Formula 44]

In addition, other monomers can be copolymerized within a range that does not impair photoreactivity and/or liquid crystalline expression ability. As said other monomer, the monomer which can obtain industrially available radical polymerization reaction is mentioned, for example. Specific examples of the other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

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

Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 ,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2 .1.0(2,6)]decyl acrylate, 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, etc. are mentioned.

Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthryl methyl methacrylate. rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 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- Propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, 8-ethyl-8-tricyclo[5.2.1.0(2,6) )] decyl methacrylate and the like.

Vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether etc. are mentioned as a specific example of the said vinyl compound.

Styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, etc. are mentioned as a specific example of the said styrene compound.

Maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned as a specific example of the said maleimide compound.

In the above side chain type polymer, the content of side chain a and side chain b is not particularly limited. The side chain a may be a 100 mol% homopolymer, or two or more types of side chain a may be used. When setting it as a copolymer of side chain a and side chain b, from a photoreactive point, 5-99.9 mol% is preferable, 5-95 mol% is more preferable, and, as for side chain a, from a viewpoint of light stability, 5-99.9 mol% is preferable. 50 mol% is more preferable. Moreover, from a viewpoint of photoreactivity, 95 mol% or less of side chain b is preferable, 5-95 mol% is more preferable, and 50 mol% or more is still more preferable from a viewpoint of light stability. Also in the case of a copolymer, you may use two or more types of side chain a and side chain b.

The side chain type polymer used in the present invention may contain other side chains. The content of the other side chains is the remainder when the sum of the contents of the side chains a and the side chains b is less than 100 mol%.

The method for producing the side chain type polymer is not particularly limited, and a general-purpose method handled industrially can be used. Specifically, it can be produced by monomer MA, if necessary, by radical polymerization, cationic polymerization, or anionic polymerization using monomer MB and vinyl groups of other monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control and the like.

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

A radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), and Sulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.) can be heard A radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioxanthone. , 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, iso Propylbenzoin 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) -butan-1-one, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid isoamyl, 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'-dimethoxy Styryl) -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)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloro) Methyl) -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-dimethylamino Propionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis(5-2,4 -Cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra (tert- Butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'- Di(tert-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(tert-butylperoxycarbonyl)benzophenone, 4,4'-di (methoxycarbonyl)-3,3'-di(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalene-2- yl-ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. are mentioned. A radical photoinitiator may be used individually by 1 type, and may mix and use 2 or more types.

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

The organic solvent used for the polymerization reaction is not particularly limited as long as the produced polymer dissolves therein. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-ε-caprolactam. , dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphate triamide, γ-butyrolactone, γ-valerolactone, isopropyl alcohol, methoxymethylpentanol, 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, dipropylene glycol monomethyl ether, diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, 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, cyclopentanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, 3-ethoxyethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, diglyme, 4-hydroxy -4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. can be heard These organic solvents may be used individually by 1 type, and may mix and use 2 or more types.

In addition, even a solvent that does not dissolve the produced polymer may be mixed with the organic solvent described above to the extent that the produced polymer does not precipitate.

Further, in radical polymerization, since oxygen in the organic solvent causes inhibition of the polymerization reaction, it is preferable to use an organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from any temperature in the range of 20 to 150°C, but is preferably in the range of 30 to 100°C. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so the monomer concentration is , Preferably it is 1-50 mass %, More preferably, it is 5-35 mass %. The initial stage of the reaction can be performed at a high concentration, and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer decreases when the ratio of the radical polymerization initiator to the monomer is large, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer increases. It is preferable that it is %. Also, various monomer components, solvents, initiators, and the like may be added during polymerization.

The polymer produced from the reaction solution obtained by the above reaction can be recovered by pouring the reaction solution into a poor solvent to precipitate it, but this reprecipitation treatment is not essential. As the poor solvent used for precipitation, methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. can be heard The polymer precipitated by being injected into a poor solvent can be collected by filtration and then dried at normal temperature or under reduced pressure by heating. In addition, if the recovered polymer is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more types of poor solvents selected from among these because the efficiency of purification is further increased.

The weight average molecular weight (Mw) of the side chain polymer used in the present invention is preferably 2,000 to 2,000,000, and preferably 2,000 to 1,000,000, considering the strength of the obtained coating film, workability during formation of the coating film, and uniformity of the coating film It is more preferable, and 5,000 to 200,000 are even more preferable. In the present invention, Mw is a value measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

The polymerizable composition used in the present invention contains the side chain polymer and an organic solvent (good solvent). The said organic solvent (good solvent) is not specifically limited if it is an organic solvent which dissolves a polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, and 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, cyclopentanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran , tetrahydrofurfuryl alcohol, etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, the said polymer composition may also contain components other than a side chain type polymer and the said organic solvent (good solvent). Examples thereof include, but are not limited to, solvents (poor 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 phase contrast film and the substrate. .

Specific examples of the solvent (poor solvent) that improves the film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl cellosolve. Solve Acetate, Ethyl Cellosolve Acetate, Butyl Carbitol, Ethyl Carbitol, Ethyl Carbitol Acetate, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, di Hexyl 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, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxy Propionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 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-ethoxypro and solvents having low surface tension such as epoxy)propanol.

The said poor solvent may be used individually by 1 type, and may mix and use 2 or more types. When using a poor solvent, the content is preferably from 5 to 80% by mass, more preferably from 10 to 60% by mass in the solvent so as not to significantly reduce the solubility of the polymer.

As a compound which improves the said film thickness uniformity or surface smoothness, a fluorochemical surfactant, silicone type surfactant, a nonionic surfactant, etc. are mentioned. Specific examples thereof include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac (registered trademark) F171, F173, F560, F563, R-30, R-40 (DIC company), Fluorad FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710 (manufactured by AGC), Suplon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 ( AGC Seimi Chemical Co., Ltd.) etc. are mentioned. The content of these surfactants is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, based on 100 parts by mass of the side chain polymer.

Specific examples of the compound that improves the adhesion between the retardation film and the substrate include functional silane-containing compounds, and specific examples thereof include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxy. Silane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3 -Aminopropyltriethoxysilane, N-(3-triethoxysilylpropyl)triethylenetetramine, N-(3-trimethoxysilylpropyl)triethylenetetramine, 10-trimethoxysilyl-1,4 ,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6 -Diazanoyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3 - Aminopropyl triethoxysilane etc. are mentioned.

In addition to improving the adhesion between the substrate and the retardation film, the polymer composition may contain a phenoplast-based compound or an epoxy group-containing compound for the purpose of preventing deterioration of properties due to backlight when forming a polarizing plate.

Specific examples of the phenoplast-based compound include those shown below, but are not limited thereto.

[Formula 45]

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclo hexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; and the like.

When using the compound which improves adhesiveness with a board|substrate, 0.1-30 mass parts is preferable with respect to 100 mass parts of side chain type polymers contained in a polymer composition, and, as for the content, 1-20 mass parts are more preferable. If the content is less than 0.1 part by mass, the effect of improving adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

As an additive, a photosensitizer can also be used. As the photosensitizer, a colorless sensitizer and a triplet sensitizer are preferable.

Examples of photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin and 7-hydroxy 4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones, and aromatic 2-hydroxyketones. -Hydroxyketone (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-methylbenzothia Zoline, 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-methylbenzooxazoline, 2-(α-naphthoylmethylene)-3-methylbenzooxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxa Zoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluoro robenzoylmethylene)-3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline, etc.), nitroacenaphthene (5-nitro acenaphthene, 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, merocumarin, and the like. Among these, aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and acetophenoneketals are preferred.

In addition to the above-mentioned polymer composition, in the range where the effect of the present invention is not impaired, for the purpose of changing electrical properties such as dielectric constant and conductivity of the retardation film, dielectrics and conductive materials, and furthermore, when used as a retardation film A crosslinkable compound may be added for the purpose of increasing the hardness and density of the film.

The polymer composition is preferably prepared as a coating liquid so as to be suitable for formation of a single-layer retardation film. That is, the polymer composition used in the present invention is obtained by dissolving a side chain polymer, a compound improving film thickness uniformity or surface smoothness, a compound improving adhesion to a substrate, and the like dissolved in an organic solvent (good solvent). It is preferably prepared as a solution.

In the said polymer composition, 1-30 mass % is preferable and, as for content of the said side chain type polymer, 3-25 mass % is more preferable.

Moreover, the said polymer composition may also contain other polymers other than the said side chain type polymer in the range which does not impair liquid-crystal expressing ability and photosensitivity performance. As said other polymer, the polymer etc. which are not photosensitive side chain type polymers which can express liquid crystal, such as poly(meth)acrylate, a polyamic acid, and a polyimide, are mentioned, for example. As for the content, when the said other polymer is included, 0.5-80 mass % is preferable in all polymer components, and 1-50 mass % is more preferable.

[Process (II)]

Step (II) is a step of irradiating the coating film with first polarized ultraviolet rays (first exposure step). When irradiating polarized ultraviolet rays to the film surface of the said coating film, polarized ultraviolet rays are irradiated through a polarizing plate from a certain direction with respect to a board|substrate.

As said ultraviolet-ray, the ultraviolet-ray of the range of 200-400 nm of wavelength can be used. Preferably, an optimal wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, it is possible to select and use ultraviolet rays within a wavelength range of 240 to 400 nm so that a photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of polarized light ultraviolet rays depends on the coating film to be used. That is, the irradiation amount is within the range of 1 to 70% of the amount of polarized ultraviolet rays that achieves the maximum value of ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the direction of the polarization axis of the polarized ultraviolet rays in the coating film and the absorbance of ultraviolet rays in the direction perpendicular to the direction. It is preferable to do it, and it is more preferable to set it in the range of 1 to 50%.

In step (II), the polarized ultraviolet rays may be irradiated from the interface side of the coating film and the air (hereinafter also referred to as the air side), or in the case of using a transparent substrate, the interface side of the coating film and the substrate (hereinafter also referred to as the substrate side). ) may be investigated.

[Process (III)]

Step (III) is a step (second exposure step) of further irradiating the coating film to which the polarized ultraviolet rays have been irradiated with second polarized ultraviolet rays having a different polarization axis direction from the first polarized ultraviolet rays. In the second polarized ultraviolet rays, the angle between the direction of the polarization axis and the direction of the polarization axis of the first polarization ultraviolet rays is preferably 10 to 80° or 100 to 170°, more preferably 20 to 70° or 110 to 160° It is preferable, and it is more preferable to be 40-70 degrees or 110-140 degrees.

In the step (III), the type of the ultraviolet rays and the irradiation amount thereof may be the same as or different from those of the step (II).

In step (III), the polarized ultraviolet rays are irradiated on the same surface as the surface to which the first polarized ultraviolet rays are irradiated in step (II). That is, when polarized ultraviolet rays are irradiated from the air side in step (II), polarized ultraviolet rays are irradiated from the air side in step (III), and polarized ultraviolet rays are irradiated from the substrate side in step (II), step In (III), polarized ultraviolet light is irradiated from the substrate side. In steps (II) and (III), it is preferable to irradiate the polarized ultraviolet rays from the air side.

As a method of irradiating second polarized ultraviolet light having a different polarization axis direction from the first polarized ultraviolet light, a polarizing plate having a polarization axis direction different from that of the polarizing plate in the first exposure step by a predetermined angle is used to irradiate second polarized ultraviolet rays. method, a method of irradiating second polarized ultraviolet rays after horizontally rotating the polarizing plate by a predetermined angle, a method of irradiating second polarized ultraviolet rays after horizontally rotating the substrate by a predetermined angle, and the like.

Further, it is preferable that the wavelengths of the ultraviolet rays irradiated in step (II) and the ultraviolet rays irradiated in step (III) are different. For example, in step (II), ultraviolet rays with a wavelength of around 313 nm are irradiated and in step (III), ultraviolet rays in the vicinity of 365 nm are irradiated, or in step (II), ultraviolet rays in the vicinity of 365 nm are irradiated and in step (III) It is preferable to irradiate ultraviolet rays of the wavelength of 313 nm vicinity. In addition, ultraviolet rays around 254 nm in step (II), ultraviolet rays around 313 nm in step (III), ultraviolet rays around 313 nm in step (II), and ultraviolet rays around 254 nm in step (III) are preferable. .

In this way, by irradiating polarized ultraviolet rays of different wavelengths in step (II) and step (III), the photoreaction state is changed on the air side and the substrate side of the single-layer retardation film, and also different in step (II) and step (III) By irradiating polarized ultraviolet rays in the direction of the polarization axis, a single-layer retardation film having different orientation axes on the air side and the substrate side can be obtained.

It is not preferable to place a heating step between steps (II) and steps (III) from the viewpoints of orientation properties and positive-wavelength dispersion suppression effect.

[Process (IV)]

The method for producing a single-layer retardation film of the present invention may include a step (IV) of heating the coating film obtained in step (III). By heating, orientation control ability can be provided to a coating film.

As a heating means, a hot plate, a heat circulation type oven, an IR (infrared ray) type oven, etc. can be used.

The heating temperature can be determined in consideration of the temperature at which the coating film to be used expresses liquid crystallinity, and the temperature at which the side chain type polymer contained in the polymerizable composition to be used expresses liquid crystallinity (hereinafter referred to as liquid crystal expression temperature) It is preferably within the temperature range. In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the surface of the coating film is expected to be lower than the liquid crystal expression temperature when the side chain type polymer is observed in bulk. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized light ultraviolet ray, the lower limit is the temperature 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer, and the upper limit is the temperature 10 ° C. lower than the upper limit of the liquid crystal temperature range. A temperature in the range of If the heating temperature is lower than the above temperature range, the amplifying effect of heat-induced anisotropy in the coating film tends to be insufficient, and if the heating temperature is excessively higher than the above temperature range, the state of the coating film is in an isotropic liquid state (isotropic phase), and in this case, it is sometimes difficult to reorient in one direction by self-organization.

In addition, the liquid crystal expression temperature is higher than the liquid crystal transition temperature at which the surface of the polymer or coating film undergoes phase transition from the solid phase to the liquid crystal phase, and isotropic phase transition temperature at which phase transition occurs from the liquid crystal phase to the isotropic phase (isotropic phase) (T _iso ) temperature below For example, expressing liquid crystal 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 single-layer retardation film produced by the production method of the present invention can be appropriately selected in consideration of the level difference and optical and electrical properties of the substrate used, and is preferably 1.0 to 10 μm, for example.

The single-layer retardation film obtained by the manufacturing method described above is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and retardation plate for organic EL or liquid crystal displays.

Example

Hereinafter, the present invention will be described in more detail by way of synthesis examples, preparation examples, examples and comparative examples, but the present invention is not limited to the following examples.

Monomers MA1, MA2 and MA3 having photoreactive groups used in Examples and monomer MB1 having liquid crystallinity are shown below. MA1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. MA2 was synthesized according to the synthesis method described in Unexamined-Japanese-Patent No. 2010-18807. MA3 was synthesized according to the synthesis method described in Unexamined-Japanese-Patent No. 2012-27354. MB1 was synthesized according to the synthesis method described in Japanese Unexamined Patent Publication No. 9-118717. MC1 was purchased from Tokyo Chemical Industry Co., Ltd. In addition, side chains derived from MA1, MA2 and MA3 correspond to side chain a, and side chains derived from MB1 correspond to side chain b. MC1 corresponds to other side chains.

[Formula 46]

In addition, the symbol of the reagent used in this Example is shown below.

(organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

(Surfactants)

R40: Megapack R-40 (DIC)

[1] Synthesis of polymers

[Synthesis Example 1]

In NMP (336 g), MA1 (36.6 g, 0.11 mol), MB1 (191 g, 0.62 mol) and AIBN (12.1 g, 0.073 mol) were dissolved to prepare a monomer mixture solution. The monomer mixed solution was added dropwise over 2 hours in NMP (224 g) at 60°C under a nitrogen atmosphere. After dripping, it was made to react at 60 degreeC for 8 hours, and the polymer fluid P1 was obtained.

[Synthesis Example 2]

In NMP (30.7 g), MA2 (2.60 g, 7.5 mmol), MB1 (13.0 g, 42.4 mmol) and AIBN (0.821 g, 5.00 mmol) were dissolved to prepare a monomer mixture solution. The monomer mixed solution was added dropwise over 2 hours in NMP (7.67 g) at 60°C under a nitrogen atmosphere. After dripping, it was made to react at 60 degreeC for 20 hours, and polymer fluid P2 was obtained.

[Synthesis Example 3]

In NMP (32.0 g), MA3 (3.29 g, 7.5 mmol), MB1 (13.0 g, 42.4 mmol) and AIBN (0.821 g, 5.00 mmol) were dissolved to prepare a monomer mixture solution. The monomer mixed solution was added dropwise over 2 hours in NMP (7.99 g) at 60°C under a nitrogen atmosphere. After dripping, it was made to react at 60 degreeC for 20 hours, and polymer fluid P3 was obtained.

[Synthesis Example 4]

In NMP (11.8 g), MA1 (0.997 g, 3.0 mmol), MB1 (4.60 g, 15.0 mmol), MC1 (0.376 g, 2.0 mmol) and AIBN (0.328 g, 2.00 mmol) were dissolved to obtain a monomer mixture solution. prepared. The monomer mixed solution was added dropwise over 2 hours in NMP (2.94 g) at 60°C under a nitrogen atmosphere. After dripping, it was made to react at 60 degreeC for 20 hours, and polymer fluid P4 was obtained.

[2] Preparation of polymer solution

[Preparation Example 1]

Polymer fluid T1 was obtained by adding and stirring NMP (4.47g), BCS (37.5g), and R40 (0.031g) to polymer fluid P1 (208g). This polymer solution T1 was used as a material for forming a phase contrast film as it was.

[Preparation Example 2]

Polymer fluid T2 was obtained by adding and stirring NMP (0.97 g), BCS (8.73 g), and R40 (7.3 mg) to polymer fluid P2 (48.5 g). This polymer solution T2 was used as a material for forming a phase contrast film as it was.

[Preparation Example 3]

Polymer fluid T3 was obtained by adding and stirring NMP (1.03 g), BCS (9.22 g) and R40 (7.7 mg) to polymer fluid P3 (51.2 g). This polymer solution T3 was used as a material for forming a phase contrast film as it was.

[Preparation Example 4]

Polymer fluid T4 was obtained by adding and stirring NMP (0.40 g), BCS (3.60 g) and R40 (3.0 mg) to polymer fluid P4 (20.0 g). This polymer solution T4 was used as a material for forming a phase contrast film as it was.

[3] Manufacture of single-layer retardation film

[Example 1]

After filtering the polymer solution T1 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 60° C. for 4 minutes to form a retardation film with a film thickness of 5.0 μm. Next, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 20 mJ/cm ² through a polarizing plate from the air side. Subsequently, the direction of the polarization axis of the first polarized ultraviolet light was set to 0°, and the substrate was rotated horizontally by 50° with respect thereto. And 100 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate (angle formed by the first polarization axis direction and the second polarization axis direction = 50°). After irradiation with polarized light ultraviolet rays twice, it was heated in a circulation oven at 140°C for 20 minutes to prepare substrate S1 with a retardation film.

[Examples 2 to 11]

Substrates S2 to S11 with a retardation film were produced in the same manner as in Example 1 except that the exposure conditions for the first or second time were changed. Detailed conditions are put together in Table 1. In the exposure conditions of Table 1, 313BPF is a 313 nm band pass filter and 365 BPF is a 365 nm band pass filter.

[Example 12]

After filtering the polymer solution T2 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 80° C. for 2 minutes to form a retardation film with a film thickness of 5.0 μm. Next, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 20 mJ/cm ² through a polarizing plate from the air side. Subsequently, the direction of the polarization axis of the first polarized ultraviolet light was set to 0°, and the substrate was rotated horizontally by 60° with respect to this direction. Then, 400 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate (angle formed by the first polarization axis direction and the second polarization axis direction = 60°). After irradiation with polarized light ultraviolet rays twice, it was heated in a circulating oven at 110°C for 20 minutes to prepare a substrate S12 with a retardation film.

[Example 13]

Substrate S13 with a retardation film was produced in the same manner as in Example 12 except that the first exposure conditions were changed. Detailed conditions are put together in Table 1.

[Example 14]

After filtering the polymer solution T3 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 80° C. for 2 minutes to form a retardation film with a film thickness of 5.0 μm. Subsequently, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 50 mJ/cm ² through a polarizing plate from the air side. Subsequently, the direction of the polarization axis of the first polarized ultraviolet light was set to 0°, and the substrate was rotated horizontally by 60° with respect to this direction. Then, ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) were irradiated at 50 mJ/cm ² from the air side through a polarizing plate (angle formed by the first polarization axis direction and the second polarization axis direction = 60°). After irradiation with polarized light ultraviolet rays twice, it was heated in a circulation oven at 130°C for 20 minutes to prepare a substrate S14 with a retardation film.

[Examples 15 to 16]

Substrates S15 to S16 with a retardation film were produced in the same manner as in Example 14 except for changing the exposure conditions for the second time. Detailed conditions are put together in Table 1.

[Example 17]

After filtering the polymer solution T4 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 80° C. for 2 minutes to form a retardation film with a film thickness of 6.0 μm. Next, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 70 mJ/cm ² through a polarizing plate from the air side. Subsequently, the direction of the polarization axis of the first polarized ultraviolet light was set to 0°, and the substrate was rotated horizontally by 50° with respect to this direction. Then, ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) were irradiated at 50 mJ/cm ² from the air side through a polarizing plate (angle formed by the first polarization axis direction and the second polarization axis direction = 50°). After irradiation with polarized light ultraviolet rays twice, it was heated for 20 minutes in a 120°C IR (infrared ray) type oven to prepare substrate S17 with a retardation film.

[Example 18, 19]

Substrates S18 and S19 with a retardation film were produced in the same manner as in Example 17, except that the exposure conditions for the first or second time were changed. Detailed conditions are put together in Table 1.

[Example 20]

After filtering the polymer solution T1 with a filter having a pore diameter of 5.0 μm, spin-coating on a cycloolefin polymer (COP) film (manufactured by Nippon Zeon Co., Ltd.) attached to a glass substrate through a double-sided tape, followed by a hot plate at 60 ° C. It was made to dry for 4 minutes on top, and the retardation film of 5.0 micrometers in thickness was formed. After pre-drying, the COP film was peeled off from the double-sided tape to obtain a polymer-coated COP film. Subsequently, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 50 mJ/cm ² through a polarizing plate from the air side. Subsequently, the direction of the polarization axis of the first polarized ultraviolet light was set to 0°, and the substrate was rotated horizontally by 60° with respect to this direction. Then, 100 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate (angle formed by the first polarization axis direction and the second polarization axis direction = 60°). After irradiation with polarized light ultraviolet rays twice, it was heated in a circulation oven at 140°C for 20 minutes to produce a COP film S20 with a retardation film.

[Comparative Example 1]

After filtering the polymer solution T1 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 60° C. for 4 minutes to form a retardation film with a film thickness of 5.0 μm. Next, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 20 mJ/cm ² through a polarizing plate from the air side. Subsequently, the angle of the substrate was adjusted so that the direction of the polarization axis of the first polarized ultraviolet light coincided with the direction of the polarization axis of the second time. Then, 100 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate. After irradiation with polarized light ultraviolet rays twice, it was heated in a circulation oven at 140°C for 20 minutes to prepare substrate R1 with a retardation film.

[Comparative Example 2]

After filtering the polymer solution T2 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 80° C. for 2 minutes to form a retardation film with a film thickness of 5.0 μm. Next, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 20 mJ/cm ² through a polarizing plate from the air side. Subsequently, the angle of the substrate was adjusted so that the direction of the polarization axis of the first polarized ultraviolet light coincided with the direction of the polarization axis of the second time. Then, 400 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate. After irradiation with polarized light ultraviolet rays twice, it was heated in a circulating oven at 110°C for 20 minutes to prepare a substrate R2 with a retardation film.

[Comparative Example 3]

After filtering the polymer solution T3 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 80° C. for 2 minutes to form a retardation film with a film thickness of 5.0 μm. Subsequently, the coating film surface was irradiated with an ultraviolet ray (313 nm band pass filter) having a wavelength of 313 nm at 50 mJ/cm ² through a polarizing plate from the air side. Subsequently, the angle of the substrate was adjusted so that the direction of the polarization axis of the first polarized ultraviolet light coincided with the direction of the polarization axis of the second time. Then, 50 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm (365 nm band pass filter) was irradiated from the air side through a polarizing plate. After irradiation with polarized light ultraviolet rays twice, it was heated in a circulation oven at 130°C for 20 minutes to prepare substrate R3 with a retardation film.

With respect to substrates S1 to S20 prepared in Examples and substrates R1 to R3 prepared in Comparative Examples, retardation values and wavelength dispersion were evaluated by the following methods.

(1) Phase difference evaluation

A linear phase difference (Linear Re) and circular phase difference (Circular Re) at a wavelength of 550 nm were evaluated using AxoScan manufactured by Axometrics. Moreover, the linear retardation (Linear Re) in a measurement wavelength of 450 nm was measured, and wavelength dispersion was evaluated by the following formula. Normal dispersion is suppressed, so that this value is small, and reverse wavelength dispersion is shown when it is less than 1.00.

Wavelength dispersion = Re[450]/Re[550]

(Re[450] represents the linear phase difference at a wavelength of 450 nm, and Re[550] represents the linear phase difference at a wavelength of 550 nm)

Table 2 below summarizes the results of phase difference evaluation and shows them. In addition, Fig. 1 shows the relationship between the linear phase difference (Linear Re) and the wavelength of the substrate with a retardation film obtained in Example 7.

Although exposure was carried out twice in Comparative Examples 1 to 3, in the retardation film having the same polarization axis direction, no original retardation was developed. On the other hand, in Examples 1 to 20 using the retardation film in which the substrate was rotated horizontally and the direction of the second polarization axis shifted from the direction of the first polarization axis, original retardation was developed. In addition, as for the wavelength dispersion of the linear retardation of Examples 1-20, normal dispersion was suppressed compared with Comparative Examples 1-3. Examples 4 to 9 and 17 to 20 showed reverse wavelength dispersion.

Comparing Example 5 and Example 11, Example 5 showed reverse wavelength dispersion, but Example 11 had normal dispersion. Therefore, it was suggested that exposure twice from the air side had a larger normal dispersion suppression effect than exposure twice from the substrate side.

(2) Evaluation of reflected color

A substrate with a retardation film was laminated on a reflector (chrome plate) so that the coated film surface was on the reflector side, and a linear polarizing plate was laminated thereon, and the reflected color was observed with the naked eye. As a result, the reflected color from the substrate of Comparative Example 1 showed a blue color, whereas the reflected color from the substrate of Example 7 showed a reflected color close to black. Therefore, the retardation film produced by this process can be applied as a retardation film for antireflection applications such as organic EL display elements.

Claims (10)

(I) a step of applying a polymer composition for forming a single-layer retardation film comprising a polymer having a photoreactive site that photoreacts with ultraviolet rays in a side chain on a substrate and drying it to form a coating film;
(II) a first exposure step of irradiating the coating film with first polarized ultraviolet rays; and
(III) a single layer including a second exposure step of irradiating a second polarized ultraviolet ray having a different polarization axis direction from the first polarized ultraviolet ray on the same surface as the surface irradiated with the first polarized ultraviolet ray to the coating film irradiated with the polarized ultraviolet ray; A method for manufacturing a phase contrast film. According to claim 1,
Further, (IV) a method for producing a single layer retardation film including a step of heating the coating film obtained in step (III). According to claim 1 or 2,
In steps (II) and (III), a method for producing a single-layer phase contrast film in which polarized ultraviolet rays are irradiated from the interface side of the coating film and air. According to any one of claims 1 to 3,
A method for producing a single-layer retardation film in which a side chain having a photoreactive site that photoreacts with the ultraviolet rays is represented by any one of the following formulas (a1) to (a6).

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.
L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also is a single bond
Y ¹ and Y ² are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and the naphthylene group are cyano groups, halogen atoms, alkyl groups of 1 to 5 carbon atoms, or alkyl groups of 2 to 6 carbon atoms It may be substituted with a carbonyl group or an alkoxy group having 1 to 5 carbon atoms.
P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms in the phenylene group are cyano groups, halogen atoms, It may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. When the number of Q ¹ is 2, each Q ¹ may be the same or different, and when the number of Q ² is 2, each Q ² may be the same or different.
R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.
X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2, each X ¹ may be the same or different, and when the number of X ² is 2, each X ² may be the same or different.
Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded thereto are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom , a C1-C5 alkyl group or a C1-C5 alkoxy group.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
G ¹ and G ² are each independently N or CH.
The dashed line is the bond hand.) According to any one of claims 1 to 4,
The manufacturing method of the single-layer phase contrast film in which the said polymer has a side chain which does neither photodimerization nor photoisomerization. According to claim 5,
The method for producing a single-layer retardation film in which the side chain that neither undergoes photodimerization nor photoisomerization is further represented by any of the following formulas (b1) to (b11).

(In the formula, A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, or -NH-C(=O)-.
R ¹ is -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 group of 5 to 8 carbon atoms, or 1 to 12 carbon atoms It is an alkyl group of or a C1-C12 alkoxy group.
R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, and some or all of the hydrogen atoms in these groups are -NO ₂ , -CN, a halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.
R ³ 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 group of 5 to 8 carbon atoms, or a carbon number It is an alkyl group of 1-12 or an alkyloxy group of 1-12 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
a is an integer of 1 to 12;
k1-k5 are each independently an integer of 0-2, but the sum of k1-k5 is 2 or more.
Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.
m1, m2 and m3 are each independently an integer of 1-3.
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 line is a bonding hand.
In addition, some or all of the hydrogen atoms of the benzene ring and naphthalene ring in the formula may be substituted with a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. .) A polymer composition for forming a single-layer retardation film comprising a polymer having a photoreactive site photoreactive with ultraviolet rays in a side chain,
(I) a step of applying the composition on a substrate and drying it to form a coating film, (II) a first exposure step of irradiating the coating film with first polarized ultraviolet rays, and (III) a coating film irradiated with the polarized ultraviolet rays , Further, by a second exposure step of irradiating second polarized ultraviolet light having a different polarization axis direction from the first polarized ultraviolet light on the same surface as the surface irradiated with the first polarized ultraviolet light, the wavelength dispersion exhibits flat dispersion or reverse wavelength dispersion. A polymer composition for forming a single-layer retardation film for providing a single-layer retardation film. According to claim 7,
The polymer composition for forming a single-layer retardation film, wherein the side chain having a photoreactive site that photoreacts with the ultraviolet rays is represented by any one of the following formulas (a1) to (a6).

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.
L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also is a single bond
Y ¹ and Y ² are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and the naphthylene group are cyano groups, halogen atoms, alkyl groups of 1 to 5 carbon atoms, or alkyl groups of 2 to 6 carbon atoms It may be substituted with a carbonyl group or an alkoxy group having 1 to 5 carbon atoms.
P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms in the phenylene group are cyano groups, halogen atoms, It may be substituted with an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. When the number of Q ¹ is 2, each Q ¹ may be the same or different, and when the number of Q ² is 2, each Q ² may be the same or different.
R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.
X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2, each X ¹ may be the same or different, and when the number of X ² is 2, each X ² may be the same or different.
Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded thereto are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom , a C1-C5 alkyl group or a C1-C5 alkoxy group.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
G ¹ and G ² are each independently N or CH.
The dashed line is the bond hand.) According to claim 8,
The polymer composition for forming a single-layer retardation film in which the above-mentioned polymer has a side chain that neither undergoes photodimerization nor photoisomerization. According to claim 9,
The polymer composition for forming a single-layer retardation film, wherein the side chain that is neither photodimerized nor photoisomerized is represented by any of the following formulas (b1) to (b11).

(In the formula, A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, or -NH-C(=O)-.
R ¹ is -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 group of 5 to 8 carbon atoms, or 1 to 12 carbon atoms It is an alkyl group of or a C1-C12 alkoxy group.
R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, and some or all of the hydrogen atoms in these groups are -NO ₂ , -CN, a halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms.
R ³ 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 group of 5 to 8 carbon atoms, or a carbon number It is an alkyl group of 1-12 or an alkyloxy group of 1-12 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
a is an integer of 1 to 12;
k1-k5 are each independently an integer of 0-2, but the sum of k1-k5 is 2 or more.
Although k6 and k7 are each independently an integer of 0-2, the sum of k6 and k7 is 1 or more.
m1, m2 and m3 are each independently an integer of 1-3.
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 line is a bonding hand.
In addition, some or all of the hydrogen atoms of the benzene ring and naphthalene ring in the formula may be substituted with a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 2 to 6 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms. .)