CN118290880A - Polymer composition and single layer phase difference material - Google Patents

Abstract

The present invention provides a polymer composition comprising (A) a side chain type polymer and (B) an organic solvent, wherein the (A) side chain type polymer comprises: a side chain having a photoreactive site represented by the following formula (a) and a side chain having a site represented by the following formula (b).

Description

Polymer composition and single layer phase difference material

The application is a divisional application of Chinese application patent application based on application number 202080020079.8, application day 2020, 3 and 26, and the application name of polymer composition and single-layer phase difference material.

Technical Field

The present invention relates to a composition comprising a polymer and a monolayer phase difference material. More specifically, the present invention relates to a material having optical characteristics suitable for applications such as display devices and recording materials, particularly a liquid crystal polymer suitable for use in optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, a composition containing the polymer, and a single-layer retardation material obtained from the composition.

Background

In view of the demands for improvement in display quality, weight reduction, and the like of liquid crystal display devices, there is an increasing demand for polymer films having controlled internal molecular alignment structures as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, films utilizing optical anisotropy possessed by polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compound used herein is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structure portion having a spacer portion and a mesogen portion), and an acryl group is widely used as the polymerizable group.

The polymerizable liquid crystal compound is usually polymerized by irradiation with radiation such as ultraviolet rays to form a polymer (film). For example, it is known that: a method of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acryl group between supports and irradiating the compound with radiation while keeping the compound in a liquid crystal state (patent document 1), and a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of 2 kinds of polymerizable liquid crystal compounds having an acryl group or a composition in which a chiral liquid crystal is mixed with the mixture and irradiating the mixture with ultraviolet rays (patent document 2).

Various single-layer coating type alignment films such as alignment films using a polymerizable liquid crystal compound and a polymer which do not require a liquid crystal alignment film (patent documents 3 and 4) and alignment films using a polymer containing a photocrosslinking site (patent documents 5 and 6) have been reported. However, the film production process is difficult, and there have been problems such as the necessity of using a solvent having excellent solubility such as NMP, chloroform, chlorobenzene, etc. as a solvent for the polymer to be used, and the low solubility of the polymer.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 62-70407

Patent document 2: japanese patent laid-open No. 9-208957

Patent document 3: european patent application publication No. 1090325 specification

Patent document 4: international publication No. 2008/031243

Patent document 5: japanese patent laid-open No. 2008-164925

Patent document 6: japanese patent laid-open No. 11-189665

Disclosure of Invention

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a novel polymer capable of producing a single-layer retardation material having a high phase difference value by a simpler process, a composition containing the polymer, and a single-layer retardation material obtained from the composition.

As a result of intensive studies to solve the above problems, the present inventors have found that a single-layer retardation material having high refractive index anisotropy (Δn) can be obtained without using a liquid crystal alignment film by using a composition containing a specific polymer and a specific additive, and that a single-layer retardation material having a high retardation value and no haze can be produced, thereby completing the present invention.

Accordingly, the present invention provides the following polymer compositions and single layer phase difference materials.

1. A polymer composition comprising (a) a side chain type polymer having: a side chain having a photoreactive site represented by the following formula (a) and a side chain having a site represented by the following formula (b); and

(B) An organic solvent.

[ Chemical formula 1]

In addition, -CH ₂CH₂ -in R ¹ may be substituted by-CH=CH-, and-CH ₂ -in R ¹ may be substituted by a group selected from-O-, -NH-C (=O) -, -C (=O) -NH-, -C (=O) -O-, -O-C (=O) -, -NH-C (=O) -NH-and-C (=O) -, wherein adjacent-CH ₂ -is not simultaneously substituted by the above-mentioned groups, -CH ₂ -may be terminal-CH ₂ -in R ¹.

R ² is a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group, or a 2-valent condensed ring group.

R ³ is a single bond, -O-, -C (=o) -O-, -O-C (=o) -or-ch=ch-C (=o) -O-.

R ⁴ is 1, 4-phenylene or trans-1, 4-cyclohexylene.

R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and when c is not less than 2, R may be the same or different from each other.

The benzene ring in the formula (b) may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group.

A is 0, 1 or 2.

B is 0 or 1.

C is an integer satisfying 0.ltoreq.c.ltoreq.2b+4.

The broken lines are the connection bonds. )

2. The polymer composition according to claim 1, wherein the side chain having a photoreactive site is a side chain represented by the following formula (a 1).

[ Chemical formula 2]

(Wherein R ¹、R² and a are the same as defined above.

R ^3A is a single bond, -O-, -C (=O) -O-or-O-C (=O) -.

The benzene ring in the formula (a 1) may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group.

The broken lines are the connection bonds. )

3. The polymer composition according to 1 or 2, wherein the side chain type polymer (A) further has side chains exhibiting only liquid crystallinity.

4. The polymer composition according to claim 3, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (12).

[ Chemical formula 3]

[ Chemical formula 4]

(Wherein a ¹、A² is each independently a single bond, -O-, -CH ₂ -, -C (=o) -O-, -O-C (=o) -, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) -O-, or-O-C (=o) -ch=ch-.

R ¹¹ is-NO ₂, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

R ¹² is a group selected from phenyl, naphthyl, biphenyl, furyl, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining the above groups, and a hydrogen atom bonded to the above group may be substituted with-NO ₂, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

R ¹³ is a hydrogen atom, -NO ₂、-CN、-CH＝C(CN)₂, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

E is-C (=O) -O-or-O-C (=o) -.

D is an integer of 1 to 12.

K1 to k5 are each independently integers of 0 to 2, and the total of k1 to k5 is 2 or more.

K6 and k7 are each independently integers of 0 to 2, and the total of k6 and k7 is 1 or more.

M1, m2 and m3 are each independently integers from 1 to 3.

N is 0 or 1.

Z ¹ and Z ² are each independently a single bond, -C (=O) -, -CH ₂ O-, -CH=N-, or-CF ₂ -.

The broken lines are the connection bonds. )

5. The polymer composition according to claim 4, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of formulas (1) to (11).

6. A method of manufacturing a single layer phase difference material, comprising:

(I) A step of forming a coating film by applying the polymer composition according to any one of 1 to 5 to a substrate;

(II) irradiating the coating film with polarized ultraviolet rays; and

(III) heating the coating film obtained by irradiating the ultraviolet ray to obtain a phase difference material.

7. A single-layer phase difference material obtained from the composition according to any one of claims 1 to 5.

The present invention can provide a single-layer retardation material having a high retardation value even for a thin film, and a polymer provided with the single-layer retardation material.

Detailed Description

The present inventors have conducted intensive studies and as a result, have obtained the following findings, thereby completing the present invention.

The polymer composition of the present invention has a photosensitive side chain polymer capable of exhibiting liquid crystallinity (hereinafter, also simply referred to as side chain polymer), and a coating film obtained using the polymer composition is a film having a photosensitive side chain polymer capable of exhibiting liquid crystallinity. The coating film was subjected to an orientation treatment by irradiation with polarized light without rubbing treatment. Then, after the irradiation of polarized light, a process of heating the side chain type polymer film is performed to obtain a film (hereinafter, also referred to as a single layer retardation material) to which optical anisotropy is imparted. At this time, the minute anisotropy exhibited by irradiation with polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is effectively reoriented by self-organization. As a result, a single-layer retardation material having high optical anisotropy can be obtained by realizing efficient alignment treatment as a single-layer retardation material.

In the polymer composition of the present invention, the side chain type polymer as component (a) includes a side chain having a photo-alignment site represented by the above formula (a) and a side chain represented by the above formula (b), thereby suppressing aggregation of the polymer. Thus, the retardation material obtained from the polymer composition of the present invention exhibits a high retardation (retardation) even in the form of a film. The inventors' findings about the mechanism of the present invention are included, and the present invention is not limited thereto.

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

[ Polymer composition ]

The polymer composition of the present invention is characterized by comprising (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a specific temperature range, and (B) an organic solvent.

[ (A) side chain type Polymer ]

(A) The component (C) is a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and has: a side chain polymer having a side chain (hereinafter, also referred to as a side chain a.) having a photoreactive site represented by the following formula (a.) and a side chain (hereinafter, also referred to as a side chain b.) having a site represented by the following formula (b.).

[ Chemical formula 5]

In the formula (a), R ¹ is an alkylene group having 1 to 30 carbon atoms, and 1 or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, -CH ₂CH₂ -in R ¹ may be substituted with-ch=ch-, and-CH ₂ -in R ¹ may be substituted with a group selected from-O-, -NH-C (=o) -, -C (=o) -NH-, -C (=o) -O-, -O-C (=o) -, -NH-C (=o) -NH-, and-C (=o) -. Wherein the adjacent-CH ₂ -is not simultaneously substituted by the above groups. Further, -CH ₂ -may be an aromatic group having a valence of 2, -alicyclic group having a valence of 2, -heterocyclic group having a valence of 2, or a condensed ring group having a valence of 2 at the terminal-CH ₂-.R² of R ¹. R ³ is a single bond, -O-, -C (=o) -O-, -O-C (=o) -or-ch=ch-C (=o) -O-. R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and when c is not less than 2, R may be the same or different from each other. a is 0, 1 or 2.b is 0 or 1.c is an integer satisfying 0.ltoreq.c.ltoreq.2b+4. The broken lines are the connection bonds.

In formula (b), R ¹、R²、R³ and a are the same as described above. R ⁴ is 1, 4-phenylene or trans-1, 4-cyclohexylene. The benzene ring in the formula (b) may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. The broken lines are the connection bonds.

The alkylene group having 1 to 30 carbon atoms represented by R ¹ may be any of straight-chain, branched-chain and cyclic, and specific examples thereof include methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl and the like.

Examples of the 2-valent aromatic group represented by R ² include phenylene and biphenylene. Examples of the alicyclic group having a valence of 2 represented by R ² include cyclohexanediyl group and the like. Examples of the heterocyclic group having a valence of 2 represented by R ² include furandiyl and the like. Examples of the condensed ring group having a valence of 2 represented by R ² include naphthylene group and the like.

The side chain a is preferably a side chain represented by the following formula (a 1) (hereinafter, also referred to as side chain a 1).

[ Chemical formula 6]

In formula (a 1), R ¹、R² and a are the same as described above. R ^3A is a single bond, -O-, -C (=O) -O-or-O-C (=O) -. The benzene ring in the formula (a 1) may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group. The broken lines are the connection bonds.

The side chain a1 is preferably a side chain represented by the following formula (a 1-1), for example.

[ Chemical formula 7]

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

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

(A) The side chain type polymer has a side chain having photosensitivity bonded to the main chain, and can induce a crosslinking reaction or an isomerization reaction by sensing light. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the above characteristics are satisfied, and a mesogen component having rigidity in the side chain structure is preferable. When the side chain type polymer is used as a single-layer retardation material, stable optical anisotropy can be obtained.

More specific examples of the structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity include a structure having a main chain and a side chain a, the main chain being composed of at least 1 radical polymerizable group selected from (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, vinyl, maleimide, norbornene and the like, and siloxane.

Further, since the side chain type polymer (a) exhibits liquid crystallinity in a temperature range of 100 to 300 ℃, it is more preferable to have a side chain exhibiting only liquid crystallinity (hereinafter, also referred to as side chain c.). Here, "exhibiting only liquid crystallinity" means that the polymer having only the side chain c exhibits only liquid crystallinity without exhibiting photo-alignment in the process for producing the phase difference material of the present invention (i.e., steps (I) to (III) described later).

The side chain c is preferably a liquid crystalline side chain selected from any one of the following formulas (1) to (12).

[ Chemical formula 8]

[ Chemical formula 9]

In the formulae (1) to (12), a ¹、A² is each independently a single bond, -O-, -CH ₂ -, -C (=o) -O-, -O-C (=o) -, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) -O-, or-O-C (=o) -ch=ch-. R ¹¹ is-NO ₂, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. R ¹² is a group selected from phenyl, naphthyl, biphenyl, furyl, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining the above groups, and a hydrogen atom bonded to the above group may be substituted with-NO ₂, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. r ¹³ is a hydrogen atom, -NO ₂、-CN、-CH＝C(CN)₂, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. E is-C (=O) -O-or-O-C (=o) -. d is an integer of 1 to 12. k1 to k5 are each independently integers of 0 to 2, and the total of k1 to k5 is 2 or more. k6 and k7 are each independently integers of 0 to 2, and the total of k6 and k7 is 1 or more. m1, m2 and m3 are each independently integers from 1 to 3. n is 0 or 1. Z ¹ and Z ² are each independently a single bond, -C (=O) -, -CH ₂ O-, -CH=N-, or-CF ₂ -. The broken lines are the connection bonds.

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

(A) The side chain type polymer of the component (a) can be obtained by polymerizing a monomer having a structure represented by the formula (a), a monomer having a structure represented by the formula (b), and a monomer having a structure exhibiting only liquid crystallinity, as desired.

The monomer having the structure represented by the formula (a) (hereinafter, also referred to as a monomer M1) includes a compound represented by the following formula (M1).

[ Chemical formula 10]

(Wherein R ¹、R²、R³, R, a, m and n are the same as those described above.)

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

[ Chemical formula 11]

(Wherein R ¹、R²、R^3A, R and a are the same as described above.)

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

[ Chemical formula 12]

(Wherein L and X are the same as those described above.)

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

[ Chemical formula 13]

In the formulae (PL-1) to (PL-5), Q ¹、Q² and Q ³ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with halogen. The dashed line is the bond to R ¹ or L. Some of the above monomers are commercially available, and some may be produced from known materials by known production methods.

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

[ Chemical formula 14]

(Wherein PL is the same as that described above, p is an integer of 2 to 9.)

The monomer having the structure represented by the formula (b) (hereinafter, also referred to as a monomer M2.) includes a compound represented by the following formula (M2).

[ Chemical formula 15]

(Wherein PL, R ¹～R⁴ and a are the same as those described above.)

As the monomer M2, a monomer represented by the following formula (M2A) is preferable.

[ Chemical formula 16]

(Wherein R ⁴, PL, L and X are the same as those described above.)

Some of the above monomers are commercially available, and some may be produced from known materials by known production methods.

The monomer having a structure exhibiting only liquid crystallinity (hereinafter, also referred to as monomer M3.) is: the polymer derived from the monomer exhibits liquid crystallinity, and the polymer is capable of forming a monomer of a mesogen group at a side chain site.

The mesogen group of the side chain may be a group having a mesogen structure such as biphenyl or phenyl benzoate alone, or may be a group having a mesogen structure such as benzoic acid by hydrogen bonding between the side chains. The mesogenic group having a side chain is preferably of the following structure.

[ Chemical formula 17]

More specific examples of the monomer M3 are preferably a structure having a structure composed of a polymerizable group derived from at least 1 kind of radical polymerizable group selected from hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, vinyl, maleimide, norbornene and the like, and at least 1 kind of siloxane in formulae (1) to (12). In particular, the monomer M3 is preferably a monomer having a (meth) acrylate as a polymerizable group, and is preferably a monomer having a side chain terminating in-COOH.

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

[ Chemical formula 18]

[ Chemical formula 19]

(Wherein PL and p are the same as those described above.)

In addition, other monomers may be copolymerized within a range that does not impair the photoreactivity and/or liquid crystal performance. Examples of the other monomer include commercially available monomers capable of undergoing radical polymerization. Specific examples of the other monomer include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, anthracene methyl acrylate, phenyl acrylate, 2-trifluoroethyl acrylate, t-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-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2-trifluoroethyl methacrylate, t-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-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like.

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

The content of the side chain a in the side chain polymer of the present invention is preferably 20 to 99.9 mol%, more preferably 30 to 95 mol%, and even more preferably 40 to 90 mol%, from the standpoint of photoreactivity.

The content of the side chain b in the side chain polymer of the present invention is preferably 0.1 to 80 mol%, more preferably 5 to 70 mol%, and even more preferably 10 to 60 mol%, from the viewpoint of the phase difference value.

The content of the side chain c in the side chain polymer of the present invention is preferably 80 mol% or less, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%, from the standpoint of photoreactivity.

As indicated above, the side chain polymers of the present invention may contain other side chains. When the total content of the side chains a to c is less than 100 mol%, the content of the other side chains is the remainder thereof.

(A) The method for producing the side chain type polymer of the component is not particularly limited, and a general method for industrial treatment can be used. Specifically, it can be produced by radical polymerization, cationic polymerization or anionic polymerization using the above-mentioned monomer M1, monomer M2, vinyl group according to the desired monomer M3 and other monomers according to the desire. Among them, radical polymerization is particularly preferred from the viewpoint of easiness of reaction control and the like.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of the radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), ketone peroxides (dibutyl cyclohexane peroxide, etc.), alkyl peresters (t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.), and the like. The radical thermal polymerization initiator may be used alone or in combination of 1 or more than 2.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of the radical photopolymerization initiator include benzophenone, michler's ketone, 4' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropenone, 2-hydroxy-2-methyl-4 ' -isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4' -di (tert-butylperoxycarbonyl) benzophenone, 3, 4' -tri (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2- (4 ' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 ',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-Methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl) ] -2, 6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2 '-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dibromophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2, 4-cyclopentan-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3', 4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (methoxycarbonyl) -4,4' -bis (t-butylperoxycarbonyl) benzophenone, 3,4 '-bis (methoxycarbonyl) -4,3' -bis (t-butylperoxycarbonyl) benzophenone, 4,4 '-bis (methoxycarbonyl) -3,3' -bis (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone, 2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) -1- (2-benzoyl) ethanone, and the like. The radical photopolymerization initiator may be used alone or in combination of 1 or more than 2.

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

The organic solvent used in the polymerization reaction is not particularly limited as long as it is an organic solvent that dissolves the polymer produced. Specific examples thereof include N, N-dimethylformamide and N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-epsilon-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methylnonone, 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 monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, propylene glycol monoacetate diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, acetic acid-3-methyl-3-methoxybutyl ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1, 4-dioxane, N-hexane, N-pentane, N-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, N-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like.

The organic solvent may be used alone or in combination of at least 2 kinds. In addition, the solvent which does not dissolve the polymer to be produced may be used in combination with the organic solvent in a range where the polymer to be produced does not precipitate. In addition, in the radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, the organic solvent is preferably used as deaerated as possible.

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

In the radical polymerization reaction, if the ratio of the radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so that the ratio of the radical initiator is preferably 0.1 to 10 mol% relative to the polymerized monomer. In addition, various monomer components, solvents, initiators, and the like may be added during polymerization.

When the polymer produced is recovered from the reaction solution obtained by the above reaction, the reaction solution is put into a poor solvent, and the polymer is precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methylethyl ether, and water. The polymer precipitated by being put into the poor solvent may be recovered by filtration and dried at normal temperature or under reduced pressure by heating at normal temperature. In addition, if the recovered polymer is re-dissolved in the organic solvent and the operation of re-precipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, and hydrocarbons, and if 3or more of the poor solvents are used, the purification efficiency is further improved, which is preferable.

In view of the strength of the resulting coating film, the workability in forming the coating film, and the uniformity of the coating film, the weight average molecular weight of the side chain type polymer (A) of the present invention measured by GPC (Gel Permeation Chromatography) method is preferably 2000 to 2000000, more preferably 2000 to 1000000, still more preferably 5000 to 200000.

[ (B) organic solvent ]

(B) The organic solvent of the component (a) is not particularly limited as long as it is an organic solvent that dissolves the polymer component. Specific examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-epsilon-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methyl ethyl ketone, methylisopentyl ketone, methylisopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate 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, and the like. The number of these may be 1 alone or 2 or more.

[ Other Components ]

The polymer composition of the present invention may contain components other than the components (a) and (B). Examples thereof include, but are not limited to, solvents or compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve adhesion of the phase difference material to the substrate, and the like.

As a specific example of the solvent (poor solvent) for improving uniformity of film thickness and surface smoothness, examples thereof include isopropyl alcohol, methoxymethyl amyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl, solvents having a low surface tension such as 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, and 2- (2-ethoxypropoxy) propanol.

The above-mentioned poor solvents may be used alone in an amount of 1 or in an amount of 2 or more. In the case of using the above-mentioned poor solvent, the content thereof is preferably 5 to 80% by mass, more preferably 20 to 60% by mass in the solvent so as not to significantly reduce the solubility of the whole solvent contained in the polymer composition.

Examples of the compound for improving film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specific examples thereof include EFTOP (registered trademark) 301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), megafac (registered trademark) F171, F173, R-30 (manufactured by DIC), FLUORAD FC430, FC431 (manufactured by 3M), asahiguard (registered trademark) AG710 (manufactured by AGC), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMI CHEMICAL), and the like. The content of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the component (a).

Specific examples of the compound for improving the adhesion between the retardation material and the substrate include a compound containing a functional silane, and specific examples thereof include 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-ureido propyl trimethoxysilane, 3-ureido propyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazadecane, 10-triethoxysilyl-1, 4, 7-triazadecane, 9-trimethoxysilyl-3, 6-diazanonylacetate, 9-triethoxysilyl-3, 6-diaza-3-methoxybenzyl-3-aminopropyl triethoxysilane, N-benzylamino-3-aminopropyl silane, N-triethoxysilane N-bis (oxyethylene) -3-aminopropyl trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane, and the like.

In addition, in order to improve the adhesion between the substrate and the phase difference material, prevent the property degradation caused by the backlight when the polarizing plate is formed, and the like, a phenolic plastic (phenoplast) compound or an epoxy group-containing compound may be added to the polymer composition.

Specific examples of the phenolic additives are shown below, but the invention is not limited thereto.

[ Chemical formula 20]

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

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

As additives, photosensitizers may also be used. As the photosensitizer, colorless sensitizers and triplet sensitizers are preferable.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), coumarin ketones, carbonylbiscoumarin, aromatic 2-hydroxyketones (2-hydroxybenzophenones, mono-or di-p- (dimethylamino) -2-hydroxybenzophenones and the like), acetophenones, anthraquinones, xanthones, thioxanthones, benzanthrone, thiazolines (2-benzoylmethylene-3-methyl- β -naphthothiazolines, 2- (. Beta. -naphthoylmethylene) -3-methylbenzothiazines, 2- (. Alpha. -dibenzoylmethylene) -3-methylbenzothiazines, 2- (. Beta. -naphthoylmethylene) -3-methyl- β -naphthothiazolines, 2- (. 4-biphenylylmethylene) -3-methyl- β -naphthothiazolines, 2- (. Beta. -fluorobenzoylmethylene) -3-naphthothiazolines), 2- (. Beta. -methylbenzothiazines and the like, and 2- (. Beta. -naphthothiazolines, 2- (. Alpha. -naphthylmethylene) -3-methylbenzoxazoline, 2- (. 4-biphenylylmethylene) -3-methylbenzoxazoline, 2- (. Beta. -naphthylmethylene) -3-methyl-. Beta. -naphthoxazoline, 2- (. P. -fluorobenzoylmethylene) -3-methyl-. Beta. -naphthoxazoline, etc.), benzothiazole, nitroaniline (meta-, para-, 4, 6-nitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthene, etc.), 2- [ (m-hydroxy-p-methoxy) styryl ] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone (2, 2-dimethoxyphenyl ethanone, etc.), naphthalene (2-naphthalenic alcohol, 2-naphthoic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracarboxylic acid, etc.), benzopyran, azoindoline, melilone, etc. Among them, aromatic 2-hydroxyketones (benzophenone), coumarin ketone, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferable.

In addition to the above-mentioned substances, a dielectric substance or a conductive substance may be added to the polymer composition of the present invention in order to change the dielectric constant, conductivity, and other electrical characteristics of the retardation material, and a crosslinkable compound may be added to improve the hardness and the density of the film when the retardation material is produced, within a range that does not impair the effects of the present invention.

[ Preparation of Polymer composition ]

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

The polymer composition of the present invention may contain other polymers in addition to the polymer of the component (A) within a range not impairing the liquid crystal display ability and photosensitivity. In this case, the content of the other polymer in the polymer component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass. Examples of the other polymer include polymers such as poly (meth) acrylate, polyamic acid, polyimide, and the like which are not photosensitive side chain polymers capable of exhibiting liquid crystallinity.

[ Single layer phase-difference Material ]

The single-layer phase difference material of the present invention can be produced by a method comprising the following steps (I) to (III).

(I) A step of forming a coating film by applying the composition of the present invention to a substrate;

(II) irradiating the coating film with polarized ultraviolet rays; and

(III) heating the coating film obtained by irradiating the ultraviolet rays to obtain a retardation material.

[ Procedure (I) ]

The step (I) is a step of forming a coating film by applying the composition of the present invention to a substrate. More specifically, the composition of the present invention is coated on a substrate (for example, a Silicon/silica-coated substrate, a Silicon nitride (Silicon nitride) substrate, a metal-coated substrate (for example, aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, an ITO substrate, etc.), a film (for example, a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, a resin film such as an acrylic film), or the like by a method such as bar coating, spin coating, flow coating, roll coating, slot coating, spin coating after slot coating, an inkjet method, a printing method, or the like. After the coating, the solvent is evaporated at 50 to 200℃and preferably 50 to 150℃by heating means such as a hot plate, a thermal circulation type oven, or an IR (infrared) type oven to obtain a coating film.

[ Procedure (II) ]

In the step (II), the coating film obtained in the step (I) is irradiated with polarized ultraviolet rays. When polarized ultraviolet rays are irradiated to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate from a constant direction through the polarizing plate. As the ultraviolet rays, ultraviolet rays having a wavelength in the range of 100 to 400nm can be used. The optimum wavelength is preferably selected via a filter or the like according to the kind of coating film used. Then, for example, in order to selectively induce a photocrosslinking reaction, ultraviolet rays having a wavelength in the range of 290 to 400nm may be selectively used. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is preferably in the range of 1 to 70% and more preferably in the range of 1 to 50% of the amount of polarized ultraviolet rays that achieve the maximum value of Δa, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of polarized ultraviolet rays in the coating film.

[ Procedure (III) ]

In the step (III), the coating film obtained by irradiating polarized ultraviolet rays in the step (II) is heated. By heating, the orientation-controlling ability can be imparted to the coating film.

Heating means such as a hot plate, a thermal circulation type oven, and an IR (infrared) type oven can be used for heating. The heating temperature can be determined in consideration of the temperature at which the coating film used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range in which the polymer of the component (a) contained in the composition of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystal exhibiting temperature). In the case of coating the surface of such a film, it is expected that the liquid crystal display temperature of the surface of the film is lower than that of the polymer of component (a) when the polymer is observed as a main body. Therefore, the heating temperature is more preferably within a temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after the irradiation of the polarized ultraviolet light is preferably a temperature in which the lower limit of the temperature range of the polymer of the component (a) is lower than the lower limit of the temperature range by 10 ℃ and the upper limit of the temperature range is lower than the upper limit of the temperature range by 10 ℃. If the heating temperature is lower than the above temperature range, there is a tendency that the effect of enhancing anisotropy of the coating film due to heat generation becomes insufficient, and if the heating temperature is too high compared with the above temperature range, there is a tendency that the state of the coating film approaches an isotropic liquid state (isotropic phase), in which case it is sometimes difficult to re-orient in one direction by self-organization.

The liquid crystal display temperature is a temperature equal to or higher than a liquid crystal transition temperature at which a polymer or a coating film surface undergoes a phase transition from a solid phase to a liquid crystal phase, and equal to or lower than an isotropic phase transition temperature (Tiso) at which a phase transition from a liquid crystal isotropic phase (isotropicphase) occurs. For example, exhibiting liquid crystallinity at 130 ℃ or lower means that the liquid crystal transition temperature at which the liquid crystal phase is phase-shifted from the solid phase to the liquid crystal phase is 130 ℃ or lower.

The thickness of the coating film formed after heating can be appropriately selected in consideration of the level difference, optical properties, and electrical properties of the substrate to be used, and is preferably, for example, 0.5 to 3 μm.

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

Examples

The present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the examples.

As the monomer having a photoreactive group used in the examples, M1 is shown below, and as the monomer having a liquid crystalline group, M2 is shown below. M1 was synthesized according to the synthesis method described in International publication No. 2011/084546. M2 was synthesized according to the synthesis method described in JP-A-9-118717. As M3, a commercially available product (M6 BC, manufactured by Midori Chemical Co., ltd.) was used. M4 is synthesized by a known method by taking 4-phenylcyclohexanone as a raw material. The side chains derived from M1 exhibited photoreactivity and liquid crystalline properties, and the side chains derived from M2 to M4 exhibited only liquid crystalline properties.

[ Chemical formula 21]

In addition, abbreviations for the reagents used in this example are shown below.

(Organic solvent)

THF: tetrahydrofuran (THF)

NMP: n-methyl-2-pyrrolidone

BCS: butyl cellosolve

BCA: butyl cellosolve acetate

PGME: propylene glycol monomethyl ether

(Polymerization initiator)

AIBN:2,2' -azobisisobutyronitrile

[1] Synthesis of methacrylate Polymer powder

Synthesis example 1

M1 (6.6 g,0.02 mol), M2 (18.4 g,0.06 mol) and M3 (7.7 g,0.02 mol) were dissolved in THF (132.7 g), and after deaeration was performed by a diaphragm pump, AIBN (0.49 g) was added and deaeration was performed again. Then, the reaction was carried out at 60℃for 8 hours to obtain a methacrylate polymer solution. The polymer solution was added dropwise to methanol (1000 mL), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure, whereby methacrylate polymer powder P1 was obtained.

Synthesis example 2

M1 (6.6 g,0.02 mol), M2 (19.9 g,0.065 mol) and M3 (5.7 g,0.015 mol) were dissolved in THF (131.2 g), and after deaeration by a diaphragm pump, AIBN (0.49 g) was added and deaeration was performed again. Then, the reaction was carried out at 60℃for 8 hours to obtain a methacrylate polymer solution. The polymer solution was added dropwise to methanol (1,000 mL), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure, whereby methacrylate polymer powder P2 was obtained.

Synthesis example 3

M1 (6.6 g,0.02 mol), M2 (12.3 g,0.04 mol) and M4 (15.5 g,0.04 mol) were dissolved in THF (139.7 g), and after deaeration by a diaphragm pump, AIBN (0.49 g) was added and deaeration was performed again. Then, the reaction was carried out at 60℃for 8 hours to obtain a methacrylate polymer solution. The polymer solution was added dropwise to methanol (1,000 mL), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure, whereby methacrylate polymer powder P3 was obtained.

Synthesis example 4

M1 (6.6 g,0.02 mol) and M2 (24.5 g,0.08 mol) were dissolved in THF (131.2 g), and after deaeration by a diaphragm pump, AIBN (0.49 g) was added to again deaerate. Then, the reaction was carried out at 60℃for 8 hours to obtain a methacrylate polymer solution. The polymer solution was added dropwise to methanol (1,000 mL), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure, whereby methacrylate polymer powder P4 was obtained.

[2] Preparation of polymer solutions

Examples 1 to 1

To NMP (3.25 g) was added methacrylate polymer powder P1 (1.5 g), and the mixture was stirred at room temperature for 1 hour to dissolve the methacrylate polymer powder P. PGME (1.5 g), BCS (3.0 g) and BCA (0.75 g) were added to the solution, followed by stirring, thereby obtaining a polymer solution T1. The polymer solution T1 is directly used as a phase difference material for forming a phase difference film.

Examples 1 to 2

To NMP (3.25 g) was added methacrylate polymer powder P2 (1.5 g), and the mixture was stirred at room temperature for 1 hour to dissolve the methacrylate polymer powder P. PGME (1.5 g), BCS (3.0 g) and BCA (0.75 g) were added to the solution, followed by stirring, thereby obtaining a polymer solution T2. The polymer solution T2 is directly used as a phase difference material for forming a phase difference film.

Examples 1 to 3

To NMP (3.25 g) was added methacrylate polymer powder P3 (1.5 g), and the mixture was stirred at room temperature for 1 hour to dissolve the methacrylate polymer powder P. PGME (1.5 g), BCS (3.0 g) and BCA (0.75 g) were added to the solution, followed by stirring, thereby obtaining a polymer solution T3. The polymer solution T3 is directly used as a phase difference material for forming a phase difference film.

Comparative example 1

To NMP (3.25 g) was added methacrylate polymer powder P4 (1.5 g), and the mixture was stirred at room temperature for 1 hour to dissolve the methacrylate polymer powder P. PGME (1.5 g), BCS (3.0 g) and BCA (0.75 g) were added to this solution, and stirred, thereby obtaining a polymer solution CT1. The polymer solution CT1 is directly used as a phase difference material for forming a phase difference film.

[3] Evaluation of Polymer solutions

Examples 2-1 to 2-3 and comparative examples 2-1 to 2-3

(1) Fabrication of evaluation substrate

The polymer solution T1 was filtered through a 0.45 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70℃for 90 seconds to form a retardation film having a film thickness of 1.0. Mu.m. Subsequently, after irradiation of 313nm ultraviolet rays of 10mJ/cm ² through a polarizing plate on the film surface, the film was heated by a hot plate at 180℃for 20 minutes, to prepare a substrate S1 with a retardation film.

Similarly, using the polymer solutions T2, T3 and CT1, substrates S2, S3 and CS1 to CS3 with retardation films having specific film thicknesses were produced at the firing temperatures shown in table 1, respectively.

(2) Evaluation of phase Difference

The phase difference values at 550nm of the substrates S1 to S3 and CS1 to CS3 were evaluated using AxoScan manufactured by Axometrics. The results are shown in Table 1.

(3) HAZE evaluation

The phase difference values at 550nm of the substrates S1 to S3 and CS1 to CS3 were evaluated using HAZE MeteR HZ-V3 manufactured by Suga tester Co. The results are shown in Table 1.

TABLE 1

Polymer solution

Substrate board

Firing temperature (. Degree. C.)

Film thickness (mum)

Phase difference value

HAZE

Example 2-1

T1

S1

180℃

1.0

130

0.09

Example 2-2

T2

S2

170℃

1.0

128

0.08

Examples 2 to 3

T3

S3

180℃

1.0

120

0.1

Comparative example 2-1

CT1

CS1

150℃

1.5

125

0.2

Comparative example 2-2

CT1

CS2

150℃

1.0

85

0.05

Comparative examples 2 to 3

CT1

CS3

180℃

1.0

15

0.05

As shown in table 1, according to the comparison of examples and comparative examples, the polymer solutions of the examples were obtained to show the results of high phase difference values also in the case of films. In addition, in the studies of comparative examples 2 to 3, it was observed that the phase difference value caused by high temperature firing was significantly reduced, and therefore it could be said that the high phase difference value in the thin film was not caused by the firing temperature.

Claims (7)

1. A polymer composition comprising:

(A) A side chain polymer having: a side chain having a photoreactive site represented by the following formula (a) and a side chain having a site represented by the following formula (b); and

(B) An organic solvent is used for the preparation of the organic solvent,

In the formulae (a) and (b), R ¹ is an alkylene group having 1 to 30 carbon atoms, 1 or more hydrogen atoms of the alkylene group are substituted with a fluorine atom or an organic group or are not substituted with a fluorine atom or an organic group, and-CH ₂CH₂ -in R ¹ is substituted with-ch=ch-or is not substituted with-ch=ch-, CH ₂ -in R ¹ is substituted with a group selected from-O-, -NH-C (=o) -, -C (=o) -NH-, -C (=o) -O-, -O-C (=o) -, -NH-C (=o) -NH-, and-C (=o) -wherein adjacent-CH ₂ -is not simultaneously substituted with the above group, and, -CH ₂ -is or is not terminal-CH ₂ in R ¹ -,

R ² is a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group, or a 2-valent condensed ring group,

R ³ is a single bond, -O-, -C (=o) -O-, -O-C (=o) -or-ch=ch-C (=o) -O-,

R ⁴ is 1, 4-phenylene or trans-1, 4-cyclohexylene,

R is alkyl with 1-6 carbon atoms, haloalkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, haloalkoxy with 1-6 carbon atoms, cyano or nitro, when c is more than or equal to 2, each R is the same or different from each other,

The benzene ring in the formula (b) is substituted or not substituted by a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group,

A is 0, 1 or 2,

B is 0 or 1 and is preferably selected from the group consisting of,

C is an integer which is more than or equal to 0 and less than or equal to 2b+4,

The broken lines are the connection bonds.

2. The polymer composition according to claim 1, wherein,

The side chain having a photoreactive site is a side chain represented by the following formula (a 1),

In the formula (a 1), R ¹、R² and a are the same as described above,

R ^3A is a single bond, -O-, -C (=O) -O-or-O-C (=O) -,

The benzene ring in the formula (a 1) is substituted or not substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group,

The broken lines are the connection bonds.

3. The polymer composition according to claim 1 or 2, wherein,

(A) The side chain type polymer also has side chains exhibiting only liquid crystallinity.

4. The polymer composition according to claim 3, wherein,

The side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (12),

In the formulae (1) to (12), a ¹、A² is each independently a single bond, -O-, -CH ₂ -, -C (=o) -O-, -O-C (=o) -, -C (=o) -NH-, -NH-C (=o) -, -ch=ch-C (=o) -O-, or-O-C (=o) -ch=ch-,

R ¹¹ is-NO ₂, -CN, halogen atom, phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group with 5-8 carbon atoms, alkyl with 1-12 carbon atoms or alkoxy with 1-12 carbon atoms,

R ¹² is a group selected from phenyl, naphthyl, biphenyl, furyl, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these groups, a hydrogen atom bonded to these groups is substituted with-NO ₂, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms or is not substituted with the above groups,

R ¹³ is a hydrogen atom, -NO ₂、-CN、-CH＝C(CN)₂, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a 1-valent nitrogen-containing heterocyclic group, a 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

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

D is an integer of 1 to 12,

K1 to k5 are each independently integers of 0 to 2, the total of k1 to k5 is 2 or more,

K6 and k7 are each independently integers of 0 to 2, the total of k6 and k7 is 1 or more,

M1, m2 and m3 are each independently an integer of 1 to 3,

N is 0 or 1, and the number of the N is not limited,

Z ¹ and Z ² are each independently a single bond, -C (=O) -, -CH ₂ O-, -CH=N-, or-CF ₂ -,

The broken lines are the connection bonds.

5. The polymer composition according to claim 4, wherein,

The side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of formulas (1) to (11).

6. A method for producing a single-layer phase difference material, comprising:

(I) A step of forming a coating film by applying the polymer composition according to any one of claims 1 to 5 to a substrate;

(II) irradiating the coating film with polarized ultraviolet rays; and

(III) heating the coating film obtained by irradiating the ultraviolet ray to obtain a phase difference material.

7. A single layer phase difference material, characterized in that it is obtained from the composition according to any one of claims 1 to 5.