CN114616518A

CN114616518A - Method for manufacturing patterned single-layer phase difference material

Info

Publication number: CN114616518A
Application number: CN202080074674.XA
Authority: CN
Inventors: 藤枝司; 根木隆之
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2019-11-05
Filing date: 2020-11-04
Publication date: 2022-06-10
Also published as: KR20220098362A; WO2021090832A1; JPWO2021090832A1; TW202134300A

Abstract

The invention provides a manufacturing method of a patterned single-layer phase difference material, which comprises the following steps: (I) a step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer onto a substrate, the liquid crystalline polymer having: a property that the orientation increases as the exposure amount is larger at exposure amounts lower than the optimum exposure amount, and the orientation decreases as the exposure amount is larger at exposure amounts higher than the optimum exposure amount; (II) irradiating the coating film obtained in the step (I) with ultraviolet rays 2 times to produce a high anisotropy region having high optical anisotropy by irradiating polarized ultraviolet rays at least 1 time while interposing a mask, and a low anisotropy region having relatively low optical anisotropy by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount and excessive in a region higher than the optimum exposure amount, wherein the irradiation is performed at least 1 time while using polarized ultraviolet rays; and (III) heating the coating film obtained in the step (II) to obtain a retardation material.

Description

Method for manufacturing patterned single-layer phase difference material

Technical Field

The present invention relates to a method for producing a patterned single-layer phase difference material and a single-layer phase difference material. More specifically, the present invention relates to a patterned single-layer retardation material obtained from a composition containing a liquid crystalline polymer, wherein the liquid crystalline polymer has: the liquid crystalline polymer has a property that the more the exposure amount is, the more the alignment is, and the liquid crystalline polymer is, and can be preferably used for a material having optical characteristics suitable for applications such as a display device and a recording material, and particularly, can be preferably used for an optical compensation film such as a polarizing plate for a liquid crystal display and a retardation plate.

Background

In response to demands for improvement in display quality and reduction in weight 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 such a demand, films obtained by utilizing the optical anisotropy of the polymerizable liquid crystal compound have been developed. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural site (a structural site having a spacer and a mesogen portion), and an acryl group is widely used as the polymerizable group.

The polymerizable liquid crystal compound is usually polymerized by a method of irradiating the polymerizable liquid crystal compound with radiation such as ultraviolet rays to form a polymer (film). For example, a method is known in which a specific polymerizable liquid crystal compound having an acryl group is supported between supports obtained by performing alignment treatment, and the compound is irradiated with radiation while being maintained in a liquid crystal state to obtain a polymer (patent document 1); a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of 2 polymerizable liquid crystal compounds having an acryl group or a composition in which a chiral liquid crystal is mixed in the mixture and irradiating ultraviolet rays (patent document 2).

Further, various single-layer coating type alignment films have been reported, such as a polymerizable liquid crystal compound that does not require a liquid crystal alignment film, an alignment film using a polymer (patent documents 3 and 4), and an alignment film using a polymer containing a photocrosslinked site (patent documents 5 and 6).

On the other hand, it is known that HAZE (HAZE) of an unexposed portion of ultraviolet rays becomes a problem when a patterned single-layer retardation film based on a polymer containing a photocrosslinked site is produced using an exposure mask in an alignment film using the material.

Documents of the prior art

Patent document

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

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

Patent document 3: european patent application publication No. 1090325

Patent document 4: international publication No. 2008/031243

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

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

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a patterned single-layer phase difference material, which can exhibit a high phase difference value in an isotropic phase by a simple process, suppress the phase difference value in the isotropic phase, and further suppress HAZE (HAZE).

Means for solving the problems

The present inventors have made extensive studies to solve the above problems, and as a result, have found that: the present inventors have found that a patterned single-layer phase difference material exhibiting a high phase difference value in an isotropic phase, suppressing the phase difference value in the isotropic phase, and further suppressing HAZE (HAZE) can be produced by applying the following method for producing a patterned phase difference material using a composition containing a specific polymer and a specific additive, and have completed the present invention.

That is, the present invention provides the following method for manufacturing a patterned single layer retardation material.

1. A method of making a patterned single layer of a phase difference material, comprising:

(I) a step of coating a polymer composition containing a liquid crystalline polymer on a substrate to form a coating film, wherein the liquid crystalline polymer comprises: a property that the orientation increases as the exposure amount is larger at exposure amounts lower than the optimum exposure amount, and the orientation decreases as the exposure amount is larger at exposure amounts higher than the optimum exposure amount;

(II) irradiating the coating film obtained in the step (I) with ultraviolet rays 2 times to produce a high anisotropy region having high optical anisotropy by irradiating polarized ultraviolet rays and a low anisotropy region having relatively low optical anisotropy by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount and excessive in a region higher than the optimum exposure amount, wherein the irradiation is performed at least 1 time while interposing a mask therebetween, and the irradiation is performed at least 1 time using polarized ultraviolet rays; and

(III) heating the coating film obtained in the step (II) to obtain a retardation material.

2. The method for producing a patterned single-layer phase difference material according to claim 1, wherein,

the polymer composition comprises:

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

(B) a silane coupling agent; and

(C) an organic solvent;

[ chemical formula 1]

In the formula, R¹An alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms in the alkylene group are optionally substituted by fluorine atoms or an organic group; furthermore, R¹In (C-CH)₂CH₂-substituted or unsubstituted-CH ═ CH-, R¹In (C-CH)₂-substituted or unsubstituted 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-CH₂-not simultaneously substituted by these groups; in addition, -CH₂-is or is not R¹terminal-CH of (1)₂-；

R²Is a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group, or a 2-valent fused cyclic group;

R³is a single bond, -O-, -C (═ O) -O-, -O-C (═ O) -or-CH ═ CH-C (═ O) -O-;

r is alkyl with 1-6 carbon atoms, halogenated alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, halogenated alkoxy with 1-6 carbon atoms, cyano or nitro, and when c is more than or equal to 2, the R are the same or different;

a is 0, 1 or 2;

b is 0 or 1;

c is an integer satisfying 0-2 b + 4;

the dotted line is the bonding site.

3. The method for producing a patterned single-layer retardation material according to claim 2, wherein the side chain having a photoreactive moiety is represented by the following formula (a1),

[ chemical formula 2]

In the formula, R¹、R²And a is the same as above;

R^3Ais a single bond, -O-, -C (═ O) -O-, or-O-C (═ O) -;

the benzene ring in the formula (a1) 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;

the dotted line is the bonding site.

4. The method for producing a patterned single-layer retardation material according to claim 2 or 3, wherein the side-chain polymer (A) further has a side chain exhibiting liquid crystallinity only.

5. The method for producing a patterned single-layer retardation material according to claim 4, wherein the side chain showing only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (13);

[ chemical formula 3]

[ chemical formula 4]

In formulae (1) to (13), A¹、A²Each independently a single bond, -O-, -CH₂-, -C (═ O) -O-, -O-C (═ O) -, -C (═ O) -NH-, -NH-C (═ O) -, -CH ═ CH-C (═ O) -O-, or-O-C (═ O) -CH ═ CH-;

R¹¹is-NO₂CN, -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;

R¹²is a group selected from phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms and a group obtained by combining the phenyl, the naphthyl, the biphenyl, the furyl, the 1-valent nitrogen-containing heterocyclic group, the 1-valent alicyclic hydrocarbon group and the 1-valent alicyclic hydrocarbon group, and a group bonded with the 1-valent alicyclic hydrocarbon group, and a hydrogen atom bonded with the 1-valent alicyclic hydrocarbon group is or is not-NO₂CN, -a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;

R¹³is a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂A 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, and an alkane having 1 to 12 carbon atomsA C1-12 alkoxy group;

e is-C (═ O) -O-or-O-C (═ O) -;

d is an integer of 1 to 12;

k1 to k5 are each independently an integer of 0 to 2, wherein the total of k1 to k5 is 2 or more;

k6 and k7 are each independently an integer of 0 to 2, wherein the total of k6 and k7 is 1 or more;

m1, m2 and m3 are each independently integers of 1-3;

n is 0 or 1;

Z¹and Z²Each independently is a single bond, -C (═ O) -, -CH₂O-, -CH-N-or-CF₂-；

The dotted line is the bonding site.

6. The method for producing a patterned single-layer retardation material according to claim 5, wherein the side chain exhibiting liquid crystallinity alone is a liquid crystalline side chain represented by any one of formulae (1) to (11).

7. A single-layer phase difference material produced by any one of the methods 1 to 6.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a patterned phase difference material that has a high phase difference value region and a low phase difference value region, and that can suppress whitening of the film in the low phase difference value region.

Detailed Description

The method for producing a patterned single-layer phase difference material of the present invention comprises the following steps [ I ] to [ III ]:

The polymer composition includes a liquid crystalline polymer having a property that the more the exposure amount is, the more the orientation increases, and the more the exposure amount is, the more the orientation decreases (hereinafter, also simply referred to as a side chain type polymer). The coating film was subjected to an alignment treatment by polarized irradiation without rubbing treatment. After the polarized irradiation, a film (hereinafter, also referred to as a single-layer retardation material) having optical anisotropy is formed through the step of heating the coating film. In this case, the slight anisotropy exhibited by the polarized irradiation forms 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 highly efficient alignment treatment.

In addition, the method for manufacturing the patterned single-layer phase difference material comprises the following steps: and irradiating the ultraviolet ray 2 times at least 1 time with polarized ultraviolet ray while interposing a mask, in such a manner that a high anisotropy region having high optical anisotropy by irradiating the polarized ultraviolet ray and a low anisotropy region having relatively low optical anisotropy by making an amount of the ultraviolet ray insufficient in a region lower than an optimum exposure amount and excessive in a region higher than the optimum exposure amount are generated, at least 1 time. By having the above steps, the film hardness is improved by irradiating ultraviolet rays both in the region having anisotropy and in the region having reduced anisotropy as compared to the region having anisotropy, and as a result, the haze, that is, the so-called whitening phenomenon, of the film can be suppressed in the region having low anisotropy in the patterned retardation material. Thus, a patterned retardation material with suppressed HAZE can be obtained.

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

[ Polymer composition ]

The polymer composition used in the production method of the present invention comprises: (A) a side chain polymer having a side chain having a photoreactive site, (B) a silane coupling agent, and (C) an organic solvent.

[ (A) side-chain type Polymer ]

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

[ chemical formula 5]

In the formula (a), R¹Is an alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. Furthermore, R¹In (C-CH)₂CH₂-may be substituted by-CH ═ CH-, R¹In (C-CH)₂-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-CH₂Are not simultaneously substituted by these groups. In addition, -CH₂May be R¹terminal-CH of (1)₂-。R²Is a 2-valent aromatic group, a 2-valent alicyclic group, a 2-valent heterocyclic group, or a 2-valent fused cyclic group. R³A 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's may be the same or different. a is 0, 1 or 2. b is 0 or 1. c is fullC is more than or equal to 0 and less than or equal to 2b + 4. The dotted line is the bonding site.

R¹The alkylene group having 1 to 30 carbon atoms may be any of a straight chain, branched chain and cyclic group, and specific examples thereof include a methylene group, an ethylene group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, a hexane-1, 6-diyl group, a heptane-1, 7-diyl group, an octane-1, 8-diyl group, a nonane-1, 9-diyl group, a decane-1, 10-diyl group and the like.

As R²The 2-valent aromatic group may include phenylene and biphenylene. As R²The alicyclic group having a valence of 2 may be cyclohexanediyl. As R²Examples of the 2-valent heterocyclic group include a furan diyl group and the like. As R²Examples of the 2-valent condensed cyclic group include naphthylene group and the like.

The side chain a is preferably a side chain represented by the following formula (a1) (hereinafter, also referred to as side chain a 1).

[ chemical formula 6]

In the formula (a1), R¹、R²And a are the same as described above. R^3AIs a single bond, -O-, -C (═ O) -O-or-O-C (═ O) -. The benzene ring in the formula (a1) 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 dotted line is the bonding site.

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

[ chemical formula 7]

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

(A) The side chain type polymer is preferably a polymer which 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 a wavelength range of 250 to 400 nm.

A side chain having photosensitivity is bonded to the main chain of the side chain type polymer (A), and can induce a crosslinking reaction or an isomerization reaction by being sensitive to light. The structure of the side chain type polymer capable of expressing photosensitivity of liquid crystallinity is not particularly limited as long as it satisfies the above characteristics, and it is preferable that the side chain structure has a rigid mesogen component. When the side chain type polymer is used as a single-layer phase difference material, stable optical anisotropy can be obtained.

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

The side chain polymer (A) preferably has a side chain (hereinafter also referred to as side chain b) which exhibits liquid crystallinity only, because it exhibits liquid crystallinity at a temperature of 100 to 300 ℃. Here, "exhibit only liquid crystallinity" means that the polymer having only the side chain b exhibits only liquid crystallinity without exhibiting photosensitivity in the process for producing the retardation material of the present invention (i.e., the steps (I) to (III) described later).

The side chain b is preferably a liquid crystalline side chain selected from any one of the following formulae (1) to (13).

[ chemical formula 8]

[ chemical formula 9]

In the formulae (1) to (13), A¹、A²Each independently a single bond, -O-, -CH₂-, -C (═ O) -O-, -O-C (═ O) -, -C (═ O) -NH-, -NH-C (═ O) -, -CH ═ CH-C (═ O) -O-, or-O-C (═ O) -CH ═ CH-. R¹¹is-NO₂CN, -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. R¹²Is a group selected from phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms and a group obtained by combining the above groups, and hydrogen atoms bonded with the above groups may be replaced by-NO₂CN, -a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R¹³Is a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH-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. E is-C (═ O) -O-or-O-C (═ O) -. d is an integer of 1 to 12; k1 to k5 are each independently an integer of 0 to 2, and the total of k1 to k5 is 2 or more. k6 and k7 are each independently an integer of 0 to 2, wherein the total of k6 and k7 is 1 or more. m1, m2 and m3 are each independently integers of 1 to 3. n is 0 or 1. Z is a linear or branched member¹And Z²Each independently is a single bond, -C (═ O) -, -CH₂O-, -CH-N-or-CF₂-. The dotted line is the bonding site.

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

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

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

[ chemical formula 10]

(in the formula, R¹、R²、R³R, a, m and n are the same as above)

The monomer M1 is preferably a monomer represented by the following formula (M1A).

[ chemical formula 11]

(in the formula, R¹、R²、R^3AR and a are the same as above)

Among the monomers M1A, a monomer represented by the following formula (M1B) is more preferable.

[ chemical formula 12]

(wherein L and X are the same as 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), Q¹、Q²And Q³The alkyl group is 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 a halogen. The dotted line is with R¹Or the bonding site of L. Among the above monomers, some are commercially available, and some can be produced from known substances by known production methods.

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

[ chemical formula 14]

(wherein PL is the same as above; p is an integer of 2 to 9)

A monomer having a structure which exhibits only liquid crystallinity (hereinafter, also referred to as a monomer M2) is a monomer which is derived from a monomer having liquid crystallinity and is capable of forming a mesogenic group in a side chain position.

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

[ chemical formula 15]

As a more specific example of the monomer M2, it is preferable to have: a structure derived from at least 1 polymerizable group selected from a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, vinyl, maleimide, norbornene, etc., and a siloxane, and a structure comprising at least 1 of formulae (1) to (13). The monomer M2 is particularly preferably a monomer having a (meth) acrylate as a polymerizable group, and is preferably a monomer having a side chain terminal of — COOH.

Preferable examples of the monomer M2 include monomers represented by the following formulas (M2-1) to (M2-11).

[ chemical formula 16]

[ chemical formula 17]

(wherein PL and p are the same as described above)

In addition, other monomers may be copolymerized within a range not impairing the expression ability of photoreactivity and/or liquid crystallinity. Examples of the other monomer include industrially available monomers capable of radical polymerization. Specific examples of the other monomer include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl methyl acrylate, phenyl acrylate, 2,2, 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-tricyclodecanyl acrylate, 8-ethyl-8-tricyclodecanyl acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, 2,2, 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, and, 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.

From the viewpoint of photoreactivity, 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 still more preferably 40 to 90 mol%.

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 still more preferably 10 to 60 mol%, from the viewpoint of a phase difference value.

As mentioned above, the side-chain polymers of the present invention may contain other side chains. The content of the other side chain is the remainder when the total content of the side chain a and the side chain b does not satisfy 100 mol%.

(A) The method for producing the side chain type polymer of the component (B) is not particularly limited, and a general method industrially employed can be used. Specifically, it can be produced by radical polymerization, cationic polymerization or anionic polymerization of a vinyl group using the above-mentioned monomer M1, monomer M2 and other monomers as desired. Among them, radical polymerization is particularly preferable from the viewpoint of easiness 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), reversible addition-fragmentation chain transfer (RAFT) polymerization reagents, and the like can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature above 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.), peroxy acetals (dibutyl peroxycyclohexane, etc.), peroxy alkyl esters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylcyclohexane, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). The radical thermal polymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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, isopropyl xanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4 ' -isopropylphenylacetone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and mixtures thereof, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, isoamyl 4-dimethylaminobenzoate, 4,4 ' -di (tert-butylperoxycarbonyl) benzophenone, 3,4,4 ' -tri (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 ' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4 ' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4 ' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-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, and mixtures thereof, 2-mercaptobenzothiazole, 3 ' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -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 ', 5,5 ' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3 ', 4,4 ' -tetrakis (tert-butylperoxycarbonyl) benzophenone, 3 ', 4,4 ' -tetrakis (tert-hexylperoxy carbonyl) benzophenone, 3 ' -bis (methoxycarbonyl) -4,4 ' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4 '-bis (methoxycarbonyl) -4, 3' -bis (tert-butylperoxycarbonyl) benzophenone, 4 '-bis (methoxycarbonyl) -3, 3' -bis (tert-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 initiators may be used in 1 kind alone or in combination of 2 or more kinds.

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 dissolves the polymer to be produced. Specific examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-epsilon-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisoamyl ketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, 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 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, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1, 4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, vinyl 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 can be used alone in 1, also can be mixed with more than 2. Further, even a solvent which does not dissolve the produced polymer may be used in combination with the organic solvent in a range where the produced polymer is not precipitated. In addition, in radical polymerization, oxygen in an organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent which is as degassed as possible.

The polymerization temperature in the radical polymerization can be selected from any temperature of 30 to 150 ℃, preferably from 50 to 100 ℃. 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, and therefore the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration at the beginning of the reaction, and then the organic solvent may be added.

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

When the polymer produced is recovered from the reaction solution obtained by the above reaction, the reaction solution may be introduced into a poor solvent to precipitate the polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by charging the poor solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or by heating. Further, if the operation of dissolving the recovered polymer in the organic solvent again and then precipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons and the like, and if 3 or more kinds of poor solvents selected from them are used, the purification efficiency is further improved, and therefore, it is preferable.

The weight average molecular weight of the side chain polymer (A) of the present invention measured by GPC (gel Permeation chromatography) method is preferably 2000 to 2000000, more preferably 2000 to 1000000, and still more preferably 5000 to 200000, in consideration of the strength of the obtained coating film, workability in forming the coating film, and uniformity of the coating film.

[ (B) silane coupling agent ]

The polymer composition of the present invention contains (B) a silane coupling agent. The silane coupling agent is preferably a silane compound represented by the following formula (B).

[ chemical formula 18]

In the formula (B), R²¹Are reactive functional groups. R²²Is a hydrolyzable group. R²³Is methyl or ethyl. x is an integer of 0 to 3. y is an integer of 1 to 3.

As R²¹Examples of the reactive functional group include an amino group, a ureido group, a (meth) acryloyloxy group, a vinyl group, an epoxy group, a mercapto group, a group having an oxetane structure, and the like, and preferred are an amino group, a ureido group, a (meth) acryloyloxy group, a group having an oxetane structure, and the like. Particularly preferred is a group having an oxetane structure.

As R²²Examples of the hydrolyzable group include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, an alkoxyalkoxy group having 2 to 4 carbon atoms, and the like. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably a straight-chain or branched-chain group, and specifically, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. The alkoxyalkoxy group having 2 to 4 carbon atoms includes, specifically, methoxymethoxy group, 2-methoxyethoxy group, ethoxymethoxy group, and 2-ethoxyethoxy group.

Specific examples of the silane coupling agent (B) include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propyltrimethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propyltriethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propylmethyldimethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propylmethyldiethoxysilane, and 3- (3-ethyloxetan-3-ylmethoxy) propylmethyldiethoxysilane.

Among them, 3- (3-ethyloxetan-3-ylmethoxy) propyltrimethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propyltriethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propylmethyldimethoxysilane, 3- (3-ethyloxetan-3-ylmethoxy) propylmethyldiethoxysilane and the like are particularly preferable. As the silane coupling agent, commercially available products can be used.

In the polymer composition of the present invention, the content of the silane coupling agent (B) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the polymer.

[ (C) organic solvent ]

(C) The organic solvent of the component (c) 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, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, 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, Methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

[ other ingredients ]

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

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include isopropyl alcohol, methoxymethylpentanol, 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 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, dipropylene glycol monoacetate monopropyl ether, and the like, Tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, diisopropyl ether, ethyl isobutyl ether, diisobutyl ether, butyl acetate, butyl butyrate, isobutyl ether, methyl cyclohexene, propyl ether, diethyl ether, 1-hexanol ether, diethyl ether, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl 3-methoxypropionate, methyl pyruvate, ethyl 3-methoxypropionate, ethyl propionate, 3-ethoxypropionate, 3-2-propyl propionate, ethyl propionate, butyl propionate, ethyl, And solvents having a low surface tension such as 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, and 2- (2-ethoxypropoxy) propanol.

The poor solvent can be used alone in 1, also can be mixed with more than 2. In the case of using the poor solvent, the content thereof in the solvent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition.

Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, examples thereof include Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products), MEGAFAC (registered trademark) F171, F173, R-30, R-40 (manufactured by DIC), FLUORAD FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710 (manufactured by AGC), SURLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC SEIMI CHEMICAL). The content of the surfactant is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the component (A).

In addition, in order to improve the adhesion between the substrate and the retardation material and to prevent the deterioration of the properties due to light such as backlight, a phenol plastic (phenoplast) compound or an epoxy group-containing compound may be added to the polymer composition.

Specific examples of the phenolic plastic-based additive are shown below, but the additive is not limited thereto.

[ chemical formula 19]

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 ' -tetraglycidyl-m-xylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) 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, and 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 is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

As additives, photosensitizers may also be used. As the photosensitizer, a leuco sensitizer and a triplet sensitizer are preferable.

Examples of the photosensitizer include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), coumarins, carbonylbiscoumarin, aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono-or di-p- (dimethylamino) -2-hydroxybenzophenone, etc.), acetophenones, anthraquinones, xanthones, thioxanthones, benzanthrone, thiazolines (2-benzoylmethylene-3-methyl- β -naphthothiazoline, 2- (. beta. -naphthoylmethylene) -3-methylbenzothiazoline, 2- (. alpha. -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenyloyl (biphenoyl) methylene) -3-methylbenzothiazoline, and mixtures thereof, 2- (beta-naphthoylmethylene) -3-methyl-beta-naphthothiazoline, 2- (4-benziylmethylene) -3-methyl-beta-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-beta-naphthothiazoline, and the like), oxazoline (2-benzoylmethylene-3-methyl-beta-naphthooxazoline, 2- (beta-naphthoylmethylene) -3-methylbenzoxazoline, 2- (alpha-naphthoylmethylene) -3-methylbenzoxazoline, 2- (4-benziylmethylene) -3-methylbenzoxazoline, 2- (beta-naphthoylmethylene) -3-methyl-beta-naphthooxazoline, or the like, 2- (4-benzimidomethylene) -3-methyl- β -naphthooxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl- β -naphthooxazoline, etc.), benzothiazole, nitroaniline (m-or p-nitroaniline, 2,4, 6-trinitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthylene, etc.), 2- [ (m-hydroxy-p-methoxy) styryl ] benzothiazole, benzoin alkyl ether, N-alkylated phthalein, acetophenone ketal (2, 2-dimethoxyacetophenone, etc.), naphthalene (2-naphthalenemethanol, 2-naphthoic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, melocoumarin, etc. Among them, aromatic 2-hydroxyketones (benzophenone), coumarins, carbonyldicumarol, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal are preferable.

In the polymer composition of the present invention, in addition to the above-mentioned substances, a dielectric substance or a conductive substance may be added in order to change electric characteristics such as a dielectric constant and conductivity of the retardation material, and a crosslinkable compound may be added in order to improve hardness and density of a film when the retardation material is produced, within a range not to 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 monolayer phase difference material. That is, the polymer composition used in the present invention is preferably prepared as a solution obtained by dissolving the component (a) and the component (B), the solvent or the compound for improving the film thickness uniformity and the surface smoothness, the compound for improving the adhesion between the liquid crystal alignment film and the substrate, and the like in the organic solvent of the component (C). The content of the component (a) in the composition of the present invention is preferably 1 to 30% 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 the photosensitivity ability. 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 other than side chain polymers capable of exhibiting liquid crystal photosensitivity, such as poly (meth) acrylate, polyamic acid, and polyimide.

[ method for producing Single-layer retardation Material ]

As described above, the method for producing a patterned single-layer retardation material of the present invention includes the following steps (I) to (III).

[ Process (I) ]

(I) The method is a step of applying a polymer composition containing a liquid crystalline polymer onto a substrate to form a coating film, wherein the liquid crystalline polymer has: the more the exposure amount is below the optimum exposure amount, the more the orientation increases, and the more the exposure amount is above the optimum exposure amount, the less the orientation decreases. More specifically, the composition is applied to a substrate (for example, a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like), a film (for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film), or the like by a method such as bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, an ink jet method, a printing method, or the like. After coating, the solvent can be evaporated by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, preferably at 50 to 200 ℃, more preferably 50 to 150 ℃, to obtain a coating film.

[ Process (II) ]

In the step (II), the coating film obtained in the step (I) is irradiated with ultraviolet rays 2 times to produce a high anisotropy region having high optical anisotropy by irradiation with polarized ultraviolet rays and a low anisotropy region having relatively low optical anisotropy by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount and excessive in a region higher than the optimum exposure amount, wherein the irradiation is performed at least 1 time while interposing a mask therebetween, and the irradiation is performed at least 1 time using polarized ultraviolet rays. More specific examples of the above-mentioned steps include the following steps (II-1) to (II-3).

[ Process (II-1) ]

In the step (II-1), the 1 st irradiation with ultraviolet light is performed through a mask so as to cover only the region to be provided with anisotropy. The ultraviolet ray in this case may be either full light ultraviolet ray or polarized ultraviolet ray. Then, the mask is removed, and polarized ultraviolet rays are irradiated. Thus, the portion covered by the mask at the 1 st irradiation is given anisotropy by irradiating only 1 st polarized ultraviolet ray, and the 2 nd ultraviolet ray irradiation is performed on the region irradiated with the 1 st ultraviolet ray, thereby reducing the anisotropy.

[ Process (II-2) ]

In the step (II-2), after the 1 st irradiation with polarized ultraviolet light, the 2 nd irradiation with ultraviolet light is performed through a mask so as to cover only the region to be provided with anisotropy. The ultraviolet ray in the 2 nd irradiation may be either full light ultraviolet ray or polarized ultraviolet ray. Thus, the portion covered by the mask at the 2 nd irradiation is given anisotropy by irradiating only 1 st polarized ultraviolet ray, and the anisotropy is reduced in the region irradiated with the 2 nd ultraviolet ray.

[ Process (II-3) ]

In the step (II-3), after the 1 st irradiation with ultraviolet light using full-gloss ultraviolet light, polarized ultraviolet light irradiation is performed for the 2 nd time through a mask so as to cover only the region where anisotropy is not to be imparted. The total light ultraviolet ray in the 1 st irradiation is preferably less than the irradiation amount of the 2 nd polarized ultraviolet ray. Thus, the portion not covered by the mask at the 2 nd irradiation is given anisotropy by the irradiation of polarized ultraviolet rays, and the anisotropy is suppressed only in the region irradiated with the 1 st ultraviolet rays.

When polarized ultraviolet light is irradiated, the substrate is irradiated with the polarized ultraviolet light from a certain direction through a polarizing plate. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100 to 400nm can be used. The optimum wavelength is preferably selected through a filter or the like according to the type of the coating film to be used. In addition, for example, in order to selectively cause the photocrosslinking reaction, can choose to use the wavelength of 290 ~ 400nm ultraviolet ray. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film used. The irradiation amount is preferably set as: the amount of polarized ultraviolet light that achieves the maximum value of Δ a (hereinafter, also referred to as Δ Amax), which is the difference between the ultraviolet light absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet light absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet light, in the coating film is in the range of 1 to 70%, more preferably in the range of 1 to 50%.

The pattern shape and pattern size of the exposure mask to be used are not particularly limited. Examples of the pattern shape include a line pattern shape, a line/space (L/S) pattern shape, a dot shape, and the like. As the pattern size, a micron-sized pattern may be formed. For example, a fine L/S pattern of about 0.5 to 500 μm can be formed by using an exposure mask having a fine pattern of an L/S pattern shape.

[ Process (III) ]

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

Heating means such as a hot plate, a thermal cycle oven, and an IR (infrared ray) oven can be used for heating. The heating temperature may be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is exhibited.

The heating temperature is preferably within a range of a temperature at which the polymer contained in the polymer composition exhibits liquid crystallinity (hereinafter referred to as a liquid crystal display temperature). In the case of a film surface such as a coating film, it is expected that the liquid crystal display temperature of the coating film surface is lower than that when the polymer is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature on the surface of the coating film. That is, the range of the heating temperature after the irradiation of the polarized ultraviolet ray is preferably a temperature in a range in which the lower limit is a temperature 10 ℃ lower than the lower limit of the range of the liquid crystal display temperature of the polymer to be used, and the upper limit is a temperature 10 ℃ lower than the upper limit of the liquid crystal temperature range. If the heating temperature is lower than the above temperature range, the effect of increasing anisotropy of the coating film by heat tends to be insufficient, and if the heating temperature is too high as compared with the above temperature range, the state of the coating film tends to be close to an isotropic liquid state (isotropic phase), and in this case, it may be difficult to perform re-orientation in one direction by self-organization.

The liquid crystal display temperature is a temperature not lower than the liquid crystal transition temperature at which the polymer or coating surface undergoes phase transition from a solid phase to a liquid crystal phase, and not higher than the isotropic phase transition temperature (Tiso) at which the liquid crystal phase undergoes phase transition to an isotropic phase. For example, the expression of liquid crystallinity at 130 ℃ or lower means that the liquid crystal transition temperature at which phase transition from a solid phase to a liquid crystal phase occurs is 130 ℃ or lower.

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

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 such as a polarizing plate for liquid crystal displays and a retardation plate.

Examples

The present invention will be described more specifically below by way of examples of synthesis, preparation, examples and comparative examples, but the present invention is not limited to the following examples.

The following are shown for M1, which is a monomer having a photoreactive group and M2, which is a monomer having a liquid crystalline group, used in examples. M1 and M2 were synthesized as follows. 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 Japanese patent application laid-open No. 9-118717. Note that the side chain derived from M1 shows photoreactivity and liquid crystallinity, and the side chain derived from M2 only has liquid crystallinity.

[ chemical formula 20]

In addition, the abbreviations of the reagents used in the present examples are shown below.

(organic solvent)

THF: tetrahydrofuran (THF)

NMP: n-ethyl-2-pyrrolidone

BCS: butyl cellosolve

PGME: propylene glycol monomethyl ether

(polymerization initiator)

AIBN: 2,2' -azobisisobutyronitrile

(polymerization initiator)

(additives)

TESOX-D: 3-Ethyl-3- [3- (triethoxysilyl) propoxymethyl ] oxetane

[ chemical formula 21]

Synthesis example Synthesis of methacrylate Polymer powder P1

M1(49.9 g: 150mmol) and M2(68.9 g: 225mmol) were dissolved in THF (482.2g), degassed with a diaphragm pump, and AIBN (1.23 g: 7.5mmol) was added and degassed again. Thereafter, the reaction was carried out at 60 ℃ for 8 hours to obtain a polymer solution of methacrylic acid ester. The polymer solution was added dropwise to a mixed solution of methanol (3020g) and pure water (1200g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure, whereby 101.1g of methacrylate polymer powder P1 was obtained.

Production example preparation of Polymer solution

To NMP (50.0g) was added methacrylate polymer powder P1(20.0g) obtained in Polymer Synthesis example P1, and the mixture was stirred at room temperature for 3 hours to dissolve it. To this solution, PGME (10.0g), BCS (20.0g), TESOX-D (1.00g) and MEGAFACE R-40(0.01g) were added and stirred, thereby obtaining a polymer solution Q1.

[ production of a phase Difference evaluation substrate ]

[ example 1]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coating surface was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion), the resultant was irradiated with 100mJ/cm of total ultraviolet light through an exposure mask having an L/S of 30 μm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R1 with a retardation film.

[ example 2]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coated film surface was irradiated with a total ultraviolet ray of 100mJ/cm through an exposure mask having an L/S value of 30 μm²(313nm conversion), the exposure mask was removed, and the mask was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R2 with a retardation film.

[ example 3]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coated surface was irradiated with total ultraviolet light at 10mJ/cm²(313nm conversion), the resultant was irradiated with polarized ultraviolet light at 20mJ/cm through an exposure mask having an L/S of 30 μm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R3 with a retardation film.

[ example 4]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet light was irradiated at 20mJ/cm in a manner perpendicular to the polarization axis of the 1 st polarized ultraviolet light through an exposure mask having an L/S of 30 μm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R4 with a retardation film.

[ example 5]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. The film was irradiated with polarized ultraviolet light at 20mJ/cm through an exposure mask having an L/S of 30 μm²(313nm conversion). Next, the exposure mask was removed, and polarized ultraviolet light was irradiated at 20mJ/cm in a manner perpendicular to the polarization axis of the 1 st polarized ultraviolet light²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R5 with a retardation film.

[ example 6]

The polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, and then spin-coated on a glass substrate having a transparent electrode, followed by drying on a hot plate at 70 ℃ for 240 seconds, thereby forming a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet light was irradiated at 100mJ/cm in parallel to the polarization axis of the 1 st polarized ultraviolet light through an exposure mask having an L/S of 30 μm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R6 with a retardation film.

[ example 7]

Filtering the polymer solution Q1 with a filter having a pore size of 5.0 μm, and then applying the solution to a transparent electrodeThe resulting film was spin-coated on a glass substrate, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet light was irradiated at 200mJ/cm in parallel to the polarization axis of the 1 st polarized ultraviolet light through an exposure mask having an L/S of 30 μm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R7 with a retardation film.

[ example 8]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the first-order polarized ultraviolet light was irradiated through an exposure mask having an L/S of 30 μm at a wavelength of 400mJ/cm so as to be parallel to the polarization axis of the 1 st-order polarized ultraviolet light²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate R8 with a retardation film.

Comparative example 1

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the film surface was irradiated with polarized ultraviolet light at 20mJ/cm through an exposure mask having an L/S of 20 μm²(313nm conversion). After exposure to polarized ultraviolet light, the substrate was heated on a hot plate at 140 ℃ for 20 minutes to obtain a substrate with a retardation film S1.

The exposure steps of examples 1 to 8 and comparative example 1 are summarized in Table 1. In examples 1,2, 4 to 8, the portions covered with the exposure mask formed high anisotropy regions (hereinafter, also referred to as anisotropic phase regions), and the portions not covered with the exposure mask formed low anisotropy regions (hereinafter, also referred to as isotropic phase regions). In example 3, the region covered by the exposure mask formed an isotropic phase.

[ Table 1]

[ production of HAZE evaluation substrate ]

[ production of substrate T1 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coating surface was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion). After the ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T1 with a retardation film. Substrate T1 is a substrate simulating the HAZE in each of the heterogeneous phase regions of examples 1 and 2, examples 4 to 8, and comparative example 1.

[ production of substrate T2 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coated surface was irradiated with total ultraviolet light at 10mJ/cm²After (313nm conversion), the sample was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T2 with a retardation film. Substrate T2 is a substrate simulating the HAZE of example 3 for each out-of-phase region.

[ production of substrate T3 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coating surface was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion), and then irradiated with total ultraviolet light of 100mJ/cm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated on a hot plate at 140 ℃ for 20 minutes to obtain a substrate with a retardation film S3. Substrate T3 is a HAZE substrate simulating the isotropic phase region of example 1.

[ production of substrate T4 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode,the resulting film was dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a thickness of 3.0. mu.m. Then, the coated surface was irradiated with total ultraviolet light at a dose of 100mJ/cm²(313nm conversion), the sample was irradiated with polarized ultraviolet light at 20mJ/cm²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T4 with a retardation film. Substrate T4 is a HAZE substrate simulating the isotropic phase region of example 2.

[ production of substrate T5 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Then, the coated surface was irradiated with total ultraviolet light at 10mJ/cm²(313nm conversion). After the ultraviolet exposure, the substrate was heated for 20 minutes by a hot plate at 140 ℃ to obtain a substrate T5 with a retardation film. Substrate T5 is a HAZE substrate simulating the isotropic phase region of example 3.

[ production of substrate T6 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet ray was irradiated at 20mJ/cm in a direction perpendicular to the polarization axis of the 1 st polarized ultraviolet ray²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T6 with a retardation film. Substrate T6 is a HAZE substrate simulating the isotropic phase region of examples 4 and 5.

[ production of substrate T7 ]

The polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, and then spin-coated on a glass substrate having a transparent electrode, followed by drying on a hot plate at 70 ℃ for 240 seconds, thereby forming a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet ray was irradiated at 100mJ/cm in parallel to the polarization axis of the 1 st polarized ultraviolet ray²(313nm conversion). After 2 UV exposures, the tape was heated for 20 minutes using a hot plate at 140 ℃ to obtain a tapeSubstrate T7 of retardation film. Substrate T7 is a HAZE substrate simulating the isotropic phase region of example 6.

[ production of substrate T8 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet ray was irradiated at 200mJ/cm in parallel to the polarization axis of the 1 st polarized ultraviolet ray²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T8 with a retardation film. Substrate T8 is a HAZE substrate simulating the isotropic phase region of example 7.

[ production of substrate T9 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Irradiating the film surface with polarized ultraviolet ray of 20mJ/cm²(313nm conversion). Then, the polarized ultraviolet light was irradiated at 400mJ/cm in parallel to the polarization axis of the 1 st polarized ultraviolet light²(313nm conversion). After 2 times of ultraviolet exposure, the substrate was heated for 20 minutes on a hot plate at 140 ℃ to obtain a substrate T9 with a retardation film. Substrate T9 is a HAZE substrate simulating the isotropic phase region of example 8.

[ production of substrate T10 ]

After the polymer solution Q1 was filtered through a filter having a pore size of 5.0. mu.m, it was spin-coated on a glass substrate having a transparent electrode, and dried on a hot plate at 70 ℃ for 240 seconds to form a retardation film having a film thickness of 3.0. mu.m. Subsequently, the substrate was heated on a hot plate at 140 ℃ for 20 minutes to obtain a substrate T10 with a retardation film. Substrate T10 is a HAZE substrate simulating the isotropic phase region of comparative example 1.

[ evaluation of retardation ]

The retardation film-attached substrates R1 to R8 and S1 were evaluated for phase difference at 550nm using an Axo Step manufactured by Axo Metrix. The results are shown in Table 2.

[ HAZE evaluation ]

The HAZEs of the substrates T1 to T10 with retardation films were evaluated using a HAZE Meter HZ-V3 manufactured by Suga test Co. The results are shown in Table 2.

[ Table 2]

As is clear from the results in table 2, in comparison of examples 1 to 8 with comparative example 1, the HAZE value in the isotropic phase region was suppressed by irradiating the isotropic phase region with ultraviolet light. However, the difference in phase difference between the isotropic phase and the anisotropic phase of examples 1 to 8 was caused due to the difference in the irradiation process. Among them, examples 4 and 5, in addition to suppression of the HAZE value, showed a large difference in phase difference between the isotropic phase and the isotropic phase, and showed a high phase difference in the isotropic phase, with very good results in which the phase difference of the isotropic phase was suppressed. Further, according to examples 6 to 8, as the exposure amount for the 2 nd polarization was increased, the phase difference value of the isotropic phase was suppressed. The reason for this is that the methacrylate polymer powder P1 has a property of reduced orientation at an exposure amount higher than the optimum exposure amount.

Industrial applicability

The method of the present invention is useful as a method for producing a patterned single-layer retardation material in which the HAZE value of the isotropic phase region is suppressed.

Claims

(I) a step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer onto a substrate, wherein the liquid crystalline polymer comprises: a property that the orientation increases as the exposure amount is larger at exposure amounts lower than the optimum exposure amount, and the orientation decreases as the exposure amount is larger at exposure amounts higher than the optimum exposure amount;

(II) a step of irradiating the coating film obtained in the step (I) with ultraviolet rays 2 times to produce a high anisotropy region having high optical anisotropy by irradiating polarized ultraviolet rays and a low anisotropy region having relatively low optical anisotropy by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount and excessive in a region higher than the optimum exposure amount, wherein the irradiation is performed at least 1 time while interposing a mask, and the irradiation is performed at least 1 time using polarized ultraviolet rays; and

2. The method of manufacturing a patterned single layer phase difference material according to claim 1,

the polymer composition comprises:

(B) a silane coupling agent; and

(C) an organic solvent;

in the formula (a), R¹An alkylene group having 1 to 30 carbon atoms, wherein 1 or more hydrogen atoms in the alkylene group are optionally substituted by fluorine atoms or an organic group; furthermore, R¹In (C-CH)₂CH₂-substituted or unsubstituted-CH ═ CH-, R¹In (C-CH)₂-substituted or unsubstituted 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-CH₂Are not simultaneously substituted by these groups; in addition, -CH₂-is or is not R¹terminal-CH of (1)₂-；

a is 0, 1 or 2;

b is 0 or 1;

c is an integer satisfying 0-2 b + 4;

the dotted line is the bonding site.

3. The method of manufacturing a patterned single layer phase difference material according to claim 2,

the side chain having a photoreactive moiety is represented by the following formula (a1),

in the formula (a1), R¹、R²And a is the same as above;

R^3Ais a single bond, -O-, -C (═ O) -O-, or-O-C (═ O) -;

the dotted line is the bonding site.

4. The method of manufacturing a patterned monolayer phase difference material according to claim 2 or 3, wherein the (A) side chain type polymer further has a side chain exhibiting only liquid crystallinity.

5. The method of manufacturing a patterned single layer phase difference material according to claim 4,

the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (13);

R¹²is a group selected from phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms and a group obtained by combining the phenyl, the naphthyl, the biphenyl, the furyl, the 1-valent nitrogen-containing heterocyclic group, the 1-valent alicyclic hydrocarbon group and the 1-valent alicyclic hydrocarbon group, and a group bonded with the 1-valent alicyclic hydrocarbon group, and a hydrogen atom bonded with the 1-valent alicyclic hydrocarbon group is or is not-NO₂CN, -a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R¹³is a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH ═ CH — CN, halogen atom, phenyl group, naphthyl group, biphenyl group, furyl group, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms;

e is-C (═ O) -O-or-O-C (═ O) -;

d is an integer of 1-12;

k 1-k 5 are each independently an integer of 0-2, wherein the total of k 1-k 5 is 2 or more;

m1, m2 and m3 are each independently integers of 1-3;

n is 0 or 1;

The dotted line is the bonding site.

6. The method of manufacturing a patterned single layer phase difference material according to claim 5,

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

7. A single-layer phase difference material produced by the method according to any one of claims 1 to 6.