WO2021090832A1 - Method for producing patterned single-layer retardation material - Google Patents

Abstract

The present invention provides a method for producing a patterned single-layer retardation material, said method comprising: (I) a step for forming a coating film by applying a polymer composition onto a substrate, said polymer composition containing a liquid crystalline polymer having properties such that the alignability increases as the amount of light exposure increases if the amount of light exposure is less than the optimal amount of light exposure, while the alignability decreases as the amount of light exposure increases if the amount of light exposure is more than the optimal amount of light exposure; (II) a step for irradiating the coating film obtained in the step (I) with ultraviolet light twice, namely at least once via a mask and at least once with use of polarized ultraviolet light so that a high anisotropy region having high optical anisotropy is produced by being irradiated with polarized ultraviolet light and a low anisotropy region having relatively low optical anisotropy is produced due to deficient ultraviolet light in a region where the amount of light exposure is less than the optimal amount of light exposure and due to excessive ultraviolet light in a region where the amount of light exposure is more than the optimal amount of light exposure; and (III) a step for obtaining a retardation material by heating the coating film obtained in the step (II).

Description

Manufacturing method of patterned single-layer retardation material

The present invention relates to a method for producing a patterned single-layer retardation material and a single-layer retardation material. Specifically, it is a liquid crystal polymer that can be suitably used for materials having optical characteristics suitable for applications such as display devices and recording materials, particularly optical compensation films such as polarizing plates and retardation plates for liquid crystal displays. It is obtained from a composition containing a polymer having a property that the orientation increases as the exposure amount increases when the exposure amount is less than the optimum exposure amount, and the orientation decreases as the exposure amount increases when the exposure amount exceeds the optimum exposure amount. The present invention relates to a patterned single-layer retardation material.

Due to the demand for improvement of display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films having a controlled internal molecular orientation structure as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, a film utilizing the optical anisotropy of the polymerizable liquid crystal compound has been developed. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group. ing.

Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of irradiating with radiation such as ultraviolet rays to polymerize. For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports subjected to orientation treatment, and the compound is kept in a liquid state and irradiated with radiation to obtain a polymer (Patent Document 1). Or, a method of adding a photopolymerization initiator to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group or a composition obtained by mixing a chiral liquid crystal with the mixture, and irradiating with ultraviolet rays to obtain a polymer (Patent Document 2). It has been known.

Further, an alignment film using a polymerizable liquid crystal compound or a polymer that does not require a liquid crystal alignment film (Patent Documents 3 and 4), an alignment film using a polymer containing a photocrosslinking site (Patent Documents 5 and 6), and the like. , Various single-layer coating type alignment films have been reported.

On the other hand, in an alignment film using a polymer containing a photocrosslinked portion, when a patterned single-layer retardation film made of the same material is produced using an exposure mask, turbidity (HAZE) in an ultraviolet unexposed portion may become a problem. It became clear.

Japanese Unexamined Patent Publication No. 62-70407 Japanese Unexamined Patent Publication No. 9-20897 European Patent Application Publication No. 1090325 International Publication No. 2008/031243 Japanese Unexamined Patent Publication No. 2008-164925 Japanese Unexamined Patent Publication No. 11-189665

The present invention has been made in view of the above problems, and by a simple process, a high retardation value is expressed in an anisotropic phase, a retardation value of an isotropic phase is suppressed, and turbidity (HAZE) is further suppressed. It is an object of the present invention to provide a method for producing a patterned single-layer retardation material.

As a result of diligent studies to solve the above problems, the present inventors apply the following method for producing a patterned retardation material using a composition containing a specific polymer and a specific additive. Therefore, they have found that it is possible to produce a patterned single-layer retardation material which expresses a high retardation value in an anisotropic phase, suppresses an isotropic phase retardation value, and further suppresses turbidity (HAZE). completed.

That is, the present invention provides a method for producing the following patterned single-layer retardation material.
1. 1. (I) A liquid crystal polymer having a property that the orientation increases as the exposure amount increases when the exposure amount is less than the optimum exposure amount, and the orientation decreases as the exposure amount increases when the exposure amount exceeds the optimum exposure amount. A step of applying a polymer composition containing a polymer having the above on a substrate to form a coating film;
(II) In the highly anisotropic region having high optical anisotropy by irradiating the coating film obtained in step (I) with polarized ultraviolet rays, and in the region where the amount of ultraviolet rays is less than the optimum exposure amount. Through the mask at least once so that a low anisotropy region having a relatively low optical anisotropy occurs due to a shortage and an excess in the region exceeding the optimum exposure amount. Patterning also includes a step of irradiating the ultraviolet rays twice with polarized ultraviolet rays at least once; and a step of heating the coating film obtained in the steps (III) and (II) to obtain a retardation material. A method for manufacturing a single-layer retardation material.
2. The polymer composition
(A) A side chain polymer having a side chain having a photoreactive site represented by the following formula (a);
(B) A method for producing a patterned single-layer retardation material, which comprises (B) a silane coupling agent; and (C) an organic solvent.

(Wherein, R ¹ is an alkylene group having 1 to 30 carbon atoms, one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Also, in R ¹ of -CH ₂ CH ₂ - is, may be substituted by -CH = CH-, -CH in R ¹ ₂ - is, -O -, - NH-C (= O) -, - C (= From O) -NH-, -C (= O) -O-, -OC (= O)-, -NH-, -NH-C (= O) -NH- and -C (= O)- It may be substituted with a group selected from the group consisting of: however, the adjacent -CH _2- dos not be substituted with these groups at the same time, and -CH _2- is the terminal-in ^{R 1.} It may be _{CH 2-.}
R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
R ³ is a single bond, -O-, -C (= O) -O-, -OC (= 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 c ≧. When 2, each R may be the same as or different from each other.
a is 0, 1 or 2.
b is 0 or 1.
c is an integer satisfying 0 ≦ c ≦ 2b + 4.
The dashed line is the bond. )
3. 3. 2. The method for producing a patterned single-layer retardation material in which the side chain having the photoreactive site is represented by the following formula (a1).

(In the formula, R ¹ , R ² and a are the same as above.
R ^3A is a single bond, -O-, -C (= O) -O- or -OC (= O)-.
The benzene ring in the formula (a1) includes 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 the like. It may be substituted with a substituent selected from nitro groups.
The dashed line is the bond. )
4. (A) A method for producing 2 or 3 patterned single-layer retardation materials in which the side chain polymer further has a side chain that expresses only liquid crystallinity.
5. The method for producing a patterned single-layer retardation material of 4, wherein the side chain expressing only the liquid crystal property is a liquid crystal side chain represented by any of the following formulas (1) to (13).

(In the equation, A ¹ and A ² are independent, single bond, -O-, -CH _2- , -C (= O) -O-, -OC (= O)-, -C (= O) -NH-, -NH-C (= O)-, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-.
R ¹¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and carbon. It is an alkyl group having a number of 1 to 12 or an alkyloxy group having a carbon number of 1 to 12.
R ¹² is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these groups. The group selected from the above, and the hydrogen atom bonded to these _{may be substituted with -NO 2} , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing complex. It is a ring group, a monovalent 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 -OC (= O)-.
d is an integer from 1 to 12.
k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more.
k6 and k7 are independently integers of 0 to 2, but the total of k6 and k7 is 1 or more.
m1, m2 and m3 are independently integers of 1 to 3.
n is 0 or 1.
Z ¹ and Z ² are independently single-bonded, -C (= O)-, -CH ₂ O-, -CH = N- or -CF _2- .
The dashed line is the bond. )
6. The method for producing a patterned single-layer retardation material according to 5, wherein the side chain expressing only liquid crystallinity is a liquid crystal side chain represented by any of the formulas (1) to (11).
A single-layer retardation material manufactured by any of the methods 7.1 to 6.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a patterned retardation material which has a region having a high retardation value and a region having a low retardation value and in which whitening of a film is suppressed in a region having a low retardation value. it can.

The method for producing a patterned single-layer retardation material of the present invention is a method including the following steps [I] to [III].
(I) A liquid crystal polymer having a property that the orientation increases as the exposure amount increases when the exposure amount is less than the optimum exposure amount, and the orientation decreases as the exposure amount increases when the exposure amount exceeds the optimum exposure amount. A step of applying a polymer composition containing a polymer having the above on a substrate to form a coating film;
(II) In the highly anisotropic region having high optical anisotropy by irradiating the coating film obtained in step (I) with polarized ultraviolet rays, and in the region where the amount of ultraviolet rays is less than the optimum exposure amount. Through the mask at least once so that a low anisotropy region having a relatively low optical anisotropy occurs due to a shortage and an excess in the region exceeding the optimum exposure amount. Further, a step of irradiating the ultraviolet rays twice with polarized ultraviolet rays at least once; and a step of heating the coating film obtained in the steps (III) and (II) to obtain a retardation material.

The polymer composition is a liquid crystal polymer, and when the exposure amount is less than the optimum exposure amount, the orientation increases as the exposure amount increases, and when the exposure amount exceeds the optimum exposure amount, the orientation increases as the exposure amount increases. The coating film obtained by using the polymer composition contains a polymer having a property of reducing the amount of light (hereinafter, also simply referred to as a side chain type polymer), and the coating film obtained by using the polymer composition is a photosensitive side chain capable of exhibiting liquidity. A film containing a type polymer. This coating film is subjected to an orientation treatment by polarization irradiation without performing a rubbing treatment. Then, after the polarization irradiation, the film is subjected to a step of heating the coating film to obtain a film having optical anisotropy (hereinafter, also referred to as a single-layer retardation material). At this time, the slight anisotropy developed by the polarization irradiation becomes the driving force, and the liquid crystal side chain polymer itself is efficiently reoriented by self-assembly. As a result, highly efficient orientation processing can be realized, and a single-layer retardation material with high optical anisotropy can be obtained.

Further, in the method for producing a patterned single-layer retardation material of the present invention, a highly anisotropic region having high optical anisotropy when irradiated with polarized ultraviolet rays and the amount of ultraviolet rays are less than the optimum exposure amount. Mask at least once so that a low anisotropy region with relatively low optical anisotropy occurs due to a shortage in the region and an excess in the region exceeding the optimum exposure. There is a step of irradiating ultraviolet rays twice with polarized ultraviolet rays at least once. By having such a step, ultraviolet irradiation is performed in both the region having anisotropy and the region where the anisotropy is less than that, and as a result of increasing the hardness of the film, the patterning position is obtained. In the retardation material, turbidity of the film in a region with low anisotropy, a so-called whitening phenomenon, can be suppressed. This makes it possible to obtain a patterned retardation material in which HAZE is suppressed.

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 contains (A) a side chain polymer having a side chain having a photoreactive moiety, (B) a silane coupling agent, and (C) an organic solvent.

[(A) Side chain polymer]
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a side chain having a photoreactive site represented by the following formula (a) (hereinafter, side chain). It is a side chain polymer having (also referred to as a).

In the formula (a), R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, -CH ₂ CH ₂ in R ¹ - it is, may be substituted by -CH = CH-, -CH ₂ in R ¹ - is, -O -, - NH-C (= O) - , -C (= O) -NH-, -C (= O) -O-, -OC (= O)-, -NH-, -NH-C (= O) -NH- and -C ( It may be substituted with a group selected from the group consisting of = O)-. However, the adjacent -CH _2- dos not be replaced by these groups at the same time. Further, -CH _2- may be the terminal -CH _{2- in} R ^1. R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. R ³ is a single bond, -O-, -C (= O) -O-, -OC (= 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 c ≧. When 2, each R may be the same as or different from each other. a is 0, 1 or 2. b is 0 or 1. c is an integer satisfying 0 ≦ c ≦ 2b + 4. The dashed line is the bond.

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

Examples of the divalent aromatic group represented by R ² include a phenylene group and a biphenylylene group. Examples of the divalent alicyclic group represented by R ^{2 include a cyclohexanediyl group and the like.} Examples of the divalent heterocyclic group represented by R ^{2 include a frangyl group and the like.} Examples of the divalent fused cyclic group represented by R ^{2 include a naphthalene group and the like.}

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

Wherein ^{(a1), R 1, R} 2 and a are as defined above. R ^3A is a single bond, -O-, -C (= O) -O- or -OC (= O)-. The benzene ring in the formula (a1) includes 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 the like. It may be substituted with a substituent selected from nitro groups. The dashed line is the bond.

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

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 —OC (= O) −.

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

The side chain polymer (A) has a photosensitive side chain bonded to the main chain, and can cause a cross-linking reaction or an isomerization reaction in response to light. The structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogen component. When the side chain 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 liquidity include (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and the like. It is preferable that the structure has a main chain composed of at least one selected from the group consisting of a radically polymerizable group such as norbornene and siloxane, and a side chain a.

Further, since the side chain type polymer (A) exhibits liquid crystallinity in a temperature range of 100 to 300 ° C., it is preferable to have a side chain (hereinafter, also referred to as side chain b) that further expresses only liquid crystallinity. .. Here, "expressing only liquid crystallinity" means that the polymer having only the side chain b is used in the process for producing the retardation material of the present invention (that is, steps (I) to (III) described later). It means that it does not show photosensitivity and only develops liquid crystallinity.

As the side chain b, any one liquid crystal side chain selected from the group consisting of the following formulas (1) to (13) is preferable.

In formulas (1) to (13), A ¹ and A ² are independently single-bonded, -O-, -CH _2- , -C (= O) -O-, -OC (= O). -, -C (= O) -NH-, -NH-C (= O)-, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH- is there. R ¹¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and carbon. It is an alkyl group having a number of 1 to 12 or an alkyloxy group having a carbon number of 1 to 12. R ¹² is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these groups. The group selected from the above, and the hydrogen atom bonded to these _{may be substituted with -NO 2} , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing complex. It is a ring group, a monovalent 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 -OC (= O)-. d is an integer from 1 to 12. k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more. k6 and k7 are independently integers of 0 to 2, but the total of k6 and k7 is 1 or more. m1, m2 and m3 are independently integers of 1 to 3. n is 0 or 1. Z ¹ and Z ² are independently single-bonded, -C (= O)-, -CH ₂ O-, -CH = N- or -CF _2- . The dashed line is the bond.

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

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

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

(In the formula, R ¹ , R ² , R ³ , R, a, m and n are the same as above.)

As the monomer M1, those represented by the following formula (M1A) are preferable.

(In the formula, R ¹ , R ² , R ^3A , R and a are the same as above.)

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

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

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

Wherein (PL-1) ~ (PL -5), Q 1, Q 2 and Q ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or straight-substituted with halogen It is a chain or branched alkyl group having 1 to 10 carbon atoms. The broken line is the bond with ^{R 1 or L.} Some of these monomers are commercially available, and some can be produced from known substances by known production methods.

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

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

A monomer having a structure that expresses only liquid crystal properties (hereinafter, also referred to as monomer M2) is a monomer in which a polymer derived from the monomer expresses liquid crystal properties and the polymer can form a mesogen group at a side chain site. That is.

As the mesogen group having a side chain, even if it is a group having a mesogen structure by itself such as biphenyl or phenylbenzoate, it is a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid. May be good. The following structure is preferable as the mesogen group contained in the side chain.

More specific examples of the monomer M2 consist of radically polymerizable groups such as hydrocarbons, (meth) acrylates, itacones, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is preferable that the structure has a structure consisting of a polymerizable group derived from at least one selected from the group and at least one of the formulas (1) to (13). In particular, the monomer M2 preferably has a (meth) acrylate as a polymerizable group, and preferably has a side chain terminal of −COOH.

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

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

Further, other monomers can be copolymerized as long as the photoreactiveness and / or liquid crystallinity expression ability is not impaired. Examples of other monomers include industrially available radical polymerization-reactive monomers. Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds, vinyl compounds and the like.

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

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

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Examples thereof include 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, propyl vinyl ether and the like. Examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene and the like. Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

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 further 40 to 90 mol% from the viewpoint of photoreactivity. preferable.

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 further preferably 10 to 60 mol% from the viewpoint of the retardation value. preferable.

As described above, the side chain polymer of the present invention may contain other side chains. The content of the other side chain is the remaining portion when the total content of the side chain a and the side chain b is less than 100 mol%.

The method for producing the side chain polymer of the component (A) is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by radical polymerization, cationic polymerization or anionic polymerization using the vinyl groups of the above-mentioned monomers M1 and M2 and, if desired, other monomers. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator (radical thermal polymerization initiator, radical photopolymerization initiator) or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent shall be used. Can be done.

The radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumenehydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.), azo radical compounds (azobisisobutyronitrile, 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile, etc.) and the like. The radical thermal polymerization initiator may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone and 2-hydroxy. -2-Methylpropiophenone, 2-Hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri ( tert-Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3' , 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [PN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-Mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-) Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3-( 2-Methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2,4- Cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) Benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3, 4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-Methyl-3H-benzothiazole-2-iriden) -1-naphthalen-2-yl-etanone, 2- (3-methyl-1,3-benzothiazole-2 (3H) -iriden) -1 -(2-Benzoyl) etanone and the like can be mentioned. The radical photopolymerization initiator may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction is not particularly limited as long as the produced polymer dissolves. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, and tetramethylurea. , Ppyridine, dimethyl sulfone, hexamethylphosphate triamide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, Methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol -Tert-Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol 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, 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, 3 -Methoxypropion Ethyl acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N Examples thereof include -dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

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

The polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 to 150 ° C, but is preferably in the range of 50 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high mass, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.

In order to recover the polymer produced from the reaction solution obtained by the above reaction, the reaction solution may be put into a poor solvent to precipitate the polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure. Further, by repeating the operation of redistributing the recovered polymer in an organic solvent and reprecipitating and recovering it 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the purification efficiency is further improved.

The side chain polymer (A) of the present invention has a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of coating film formation, and uniformity of the coating film. However, it is preferably 2,000 to 2,000,000, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 200,000.

[(B) Silane coupling agent]
The polymer composition of the present invention contains (B) a silane coupling agent. As the silane coupling agent, a silane compound represented by the following formula (B) is preferable.

In formula (B), R ²¹ is a reactive functional group. R ²² is a hydrolyzable group. R ²³ is a methyl group or an ethyl group. x is an integer of 0 to 3. y is an integer of 1 to 3.

Examples of the reactive functional group represented by R ²¹ include an amino group, a ureido group, a (meth) acryloxy group, a vinyl group, an epoxy group, a mercapto group and a group having an oxetane structure, and examples thereof include an amino group, a ureido group, and a group having an oxetane structure. (Meta) Acryloyloxy groups, groups having an oxetane structure and the like are preferable. Particularly preferably, it is a group having an oxetane structure.

Examples of the hydrolyzable group represented by R ²² include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically, it is a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms are a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group and a 2-ethoxyethoxy group.

(B) Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldi. Ethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-( 3-Ethyloxetane-3-ylmethyloxy) Propyltrimethoxysilane, 3- (3-ethyloxetane-3-ylmethyloxy) propyltriethoxysilane, 3- (3-ethyloxetane-3-ylmethyloxy) propyl Examples thereof include methyldimethoxysilane and 3- (3-ethyloxetane-3-ylmethyloxy) propylmethyldiethoxysilane.

Of these, 3- (3-ethyloxetane-3-ylmethyloxy) propyltrimethoxysilane, 3- (3-ethyloxetane-3-ylmethyloxy) propyltriethoxysilane, 3- (3-ethyloxetane-) 3-Ilmethyloxy) propylmethyldimethoxysilane, 3- (3-ethyloxetane-3-ylmethyloxy) propylmethyldiethoxysilane and the like are particularly preferable. As the silane coupling agent, a commercially available product can be used.

The content of the (B) silane coupling agent in the polymer composition of the present invention is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the polymer. More preferably, 0.05 to 1 part by mass.

[(C) Organic solvent]
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, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-. Vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphate triamide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropaneamide, 3-ethoxy-N, N-dimethylpropane Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene Examples thereof include carbonate, diglime, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used individually by 1 type, or may be used by mixing 2 or more types.

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

Specific examples of the solvent (poor solvent) that improves the uniformity of film thickness and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl carbitol. , Ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, di Propropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl buty Rate, 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 lactate -Butyl, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol Examples thereof include solvents having a low surface tension such as col-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, and 2- (2-ethoxypropoxy) propanol.

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

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafuck (registered trademark) F171, F173, R-30, R-40 (manufactured by DIC), and Florard. FC430, FC431 (manufactured by 3M), Asahi Guard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical), etc. Can be mentioned. The content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A).

Further, in addition to improving the adhesion between the substrate and the retardation material, even if a phenoplast-based compound or an epoxy group-containing compound is added to the polymer composition for the purpose of preventing deterioration of characteristics due to light such as a backlight. Good.

Specific examples of the phenoplast-based additive are shown below, but the present invention is not limited thereto.

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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Can be mentioned.

When a compound that improves the adhesion to the substrate is used, the content thereof is preferably 0.1 to 30 parts by mass and 1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition. Is more preferable. If the content is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may deteriorate.

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

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone (2-hydroxybenzophenone, Mono- or di-p- (dimethylamino) -2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xantone, thioxanthone, benzanthron, thiazolin (2-benzoylmethylene-3-methyl-β-naphthothiazolin, 2- (β) -Naftylmethylene) -3-methylbenzothiazolin, 2- (α-naphthoylmethylene) -3-methylbenzothiazolin, 2- (4-biphenoylmethylene) -3-methylbenzothiazolin, 2- (β-naphtho) Ilmethylene) -3-methyl-β-naphthiazolin, 2- (4-biphenoylmethylene) -3-methyl-β-naphthiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthiazoline Etc.), Oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) -3-methylbenzoxazoline , 2- (4-Bifenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoylmethylene) -3-methyl- β-Naftoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline, etc.) ), Nitroacenaften (5-nitroacenaften, etc.), 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl) (Etanone, etc.), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindidine, merocmarin and the like. Of these, aromatic 2-hydroxyketones (benzophenone), coumarin, ketocoumarin, carbonyl biscumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetal phenone ketal are preferred.

In addition to the above-mentioned ones, the polymer composition of the present invention includes a dielectric material for the purpose of changing the electrical characteristics such as the dielectric constant and conductivity of the retardation material as long as the effects of the present invention are not impaired. A crosslinkable compound may be added for the purpose of increasing the hardness and the density of the film when it is used as a conductive substance or a retardation material.

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

The polymer composition of the present invention may contain other polymers in addition to the polymer of the component (A) as long as the liquid crystal expression ability and the photosensitive performance are not impaired. At that time, 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 other polymers include polymers such as poly (meth) acrylate, polyamic acid, and polyimide, which are not photosensitive side chain polymers capable of exhibiting liquid crystallinity.

[Manufacturing method of 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).
(I) A liquid crystal polymer having a property that the orientation increases as the exposure amount increases when the exposure amount is less than the optimum exposure amount, and the orientation decreases as the exposure amount increases when the exposure amount exceeds the optimum exposure amount. A step of applying a polymer composition containing a polymer having the above on a substrate to form a coating film;
(II) In the highly anisotropic region having high optical anisotropy by irradiating the coating film obtained in step (I) with polarized ultraviolet rays, and in the region where the amount of ultraviolet rays is less than the optimum exposure amount. Through the mask at least once so that a low anisotropy region having a relatively low optical anisotropy occurs due to a shortage and an excess in the region exceeding the optimum exposure amount. Further, a step of irradiating the ultraviolet rays twice with polarized ultraviolet rays at least once; and a step of heating the coating film obtained in the steps (III) and (II) to obtain a retardation material.

[Step (I)]
The step (I) is a liquid crystal polymer, and when the exposure amount is less than the optimum exposure amount, the orientation increases as the exposure amount increases, and when the exposure amount exceeds the optimum exposure amount, the orientation increases as the exposure amount increases. This is a step of applying a polymer composition containing a polymer having a reducing property onto a substrate to form a coating film. More specifically, the composition is coated on a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate). Etc.) and films (for example, resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film), etc., bar coat, spin coat, flow coat, roll coat, slit coat , Slit coating followed by spin coating, inkjet method, printing method, etc. After coating, the solvent is evaporated at preferably 50 to 200 ° C., more preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven to obtain a coating film. Can be done.

[Step (II)]
In step (II), the coating film obtained in step (I) is irradiated with polarized ultraviolet rays in a highly anisotropic region having high optical anisotropy and in a region where the amount of ultraviolet rays is less than the optimum exposure amount. At least once through the mask so that there is a low anisotropy region with relatively low optical anisotropy due to a shortage and an excess in the region above the optimum exposure. At least once, polarized ultraviolet rays are used to irradiate the ultraviolet rays twice. More specific embodiments of such a step include the following steps (II-1) to (II-3).

[Step (II-1)]
In step (II-1), the first ultraviolet irradiation is performed through a mask so that only the region to which anisotropy is desired to be imparted is covered. The ultraviolet rays at this time may be all-light ultraviolet rays or polarized ultraviolet rays. Next, the mask is removed and polarized ultraviolet rays are irradiated. As a result, the portion covered with the mask at the time of the first irradiation is irradiated with polarized ultraviolet rays only once to impart anisotropy, and the region subjected to the first ultraviolet irradiation is subjected to the second ultraviolet rays. Irradiation reduces anisotropy.

[Step (II-2)]
In the step (II-2), after the first ultraviolet irradiation using polarized ultraviolet rays, the second ultraviolet irradiation is performed through a mask so that only the region to which anisotropy is desired to be imparted is covered. The ultraviolet rays at the time of the second irradiation may be all-light ultraviolet rays or polarized ultraviolet rays. As a result, the portion covered with the mask during the second irradiation is anisotropyed by being irradiated with polarized ultraviolet rays only once, and the region subjected to the second irradiation is anisotropy. Decreases.

[Step (II-3)]
In step (II-3), after the first irradiation with ultraviolet rays using all-light ultraviolet rays, the second irradiation with polarized ultraviolet rays is performed through a mask so that only the region to which anisotropy is not desired to be imparted is covered. Do. The total light ultraviolet rays at the time of the first irradiation are preferably smaller than the second polarized ultraviolet rays. As a result, the portion not covered by the mask during the second irradiation is irradiated with polarized ultraviolet rays to impart anisotropy, and the region subjected to only the first ultraviolet irradiation is anisotropy. It is suppressed.

When irradiating polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays from a certain direction through a polarizing plate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film used. Then, for example, ultraviolet rays having a wavelength in the range of 290 to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. 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 the amount of polarized ultraviolet rays that realizes the maximum value of ΔA (hereinafter, also referred to as ΔAmax), which is the difference between the ultraviolet absorptance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorptivity in the vertical direction in the coating film. The amount is preferably 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 used are not particularly limited. Examples of the pattern shape include a line pattern shape, a line / space (L / S) pattern shape, and a dot shape. As the pattern size, a micrometer-sized pattern can be formed. For example, by using an exposure mask having a fine pattern having an L / S pattern shape, a fine L / S pattern of about 0.5 to 500 μm can be formed.

[Step (III)]
In step (III), the coating film irradiated with polarized ultraviolet rays in step (II) is heated. Orientation control ability can be imparted to the coating film by heating.

For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is exhibited.

The heating temperature is preferably within the range of the temperature at which the polymer contained in the polymer composition exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when the polymer is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the range of the heating temperature after irradiation with polarized ultraviolet rays is a range in which the lower limit is 10 ° C lower than the lower limit of the liquid crystal development temperature range of the polymer to be used, and the upper limit is the temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. The temperature is preferably. If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high above the above temperature range, the state of the coating film is in a state. Tends to be close to an isotropic liquid state (isotropic phase), in which case self-assembly can make it difficult to reorient in one direction.

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

The thickness of the coating film formed after heating can be appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties, 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 in particular, polarizing plates and retardation plates for liquid crystal displays and the like. It is suitable as an optical compensation film.

Hereinafter, the present invention will be described in more detail with reference to synthetic examples, preparation examples, examples and comparative examples, but the present invention is not limited to the following examples.

M1 which is a monomer having a photoreactive group and M2 which is a monomer having a liquid crystal group used in the examples are shown below. M1 and M2 were synthesized as follows, respectively. M1 was synthesized according to the synthetic method described in International Publication No. 2011/0854546. M2 was synthesized according to the synthesis method described in JP-A-9-118717. The side chain derived from M1 exhibits photoreactivity and liquid crystallinity, and the side chain derived from M2 has only liquid crystallinity.

In addition, the abbreviations of the reagents used in this example are shown below.
(Organic solvent)
THF: Tetrahydrofuran NMP: N-Ethyl-2-pyrrolidone BCS: Butyl cellosorb PGME: Propylene glycol monomethyl ether

(Polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile

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

[Synthetic example] Synthesis of methacrylate polymer powder P1 M1 (49.9 g: 150 mmol) and M2 (68.9 g: 225 mmol) were dissolved in THF (482.2 g), degassed with a diaphragm pump, and then AIBN. (1.23 g: 7.5 mmol) was added and degassing was performed again. Then, the reaction was carried out at 60 ° C. for 8 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to a mixed solution of methanol (3,020 g) and pure water (1,200 g), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure to obtain 101.1 g of methacrylate polymer powder P1.

[Preparation Example] Preparation of Polymer Solution The methacrylate polymer powder P1 (20.0 g) obtained in Polymer Synthesis Example P1 was added to NMP (50.0 g), and the mixture was dissolved by stirring at room temperature for 3 hours. To this solution, PGME (10.0 g), BCS (20.0 g), TESOX-D (1.00 g) and Megafuck R-40 (0.01 g) were added and stirred to obtain a polymer solution Q1. ..

[Manufacturing of phase difference value evaluation board]
[Example 1]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion), and then all-light ultraviolet rays were irradiated at 100 mJ / cm ² (313 nm conversion) through an exposure mask having L / S = 30 μm. After two UV exposures, the substrate R1 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes.

[Example 2]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. ^{Next, after irradiating the coating film surface with 100 mJ / cm 2} (313 nm conversion) of total light ultraviolet rays through an exposure mask having L / S = 30 μm, the exposure mask is removed and polarized ultraviolet rays are 20 mJ / cm ² (313 nm conversion). Irradiated. After two UV exposures, the substrate R2 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes.

[Example 3]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, after irradiating the coating film surface with total light ultraviolet rays at 10 mJ / cm ² (313 nm conversion), polarized ultraviolet rays were irradiated at 20 mJ / cm ² (313 nm conversion) through an exposure mask having L / S = 30 μm. After two exposures to ultraviolet rays, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate R3 with a retardation film.

[Example 4]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 20 mJ / cm 2} (313 nm conversion) so as to be perpendicular to the polarization axis of the first polarized ultraviolet rays through an exposure mask having L / S = 30 μm. After two exposures to ultraviolet rays, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate R4 with a retardation film.

[Example 5]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. ^{The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm 2} (in terms of 313 nm) through an exposure mask having L / S = 30 μm. Subsequently, the exposure mask was removed, and polarized ultraviolet rays were irradiated at 20 mJ / cm ² (313 nm conversion) so as to be perpendicular to the polarization axis of the first polarized ultraviolet rays. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes 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 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 100 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays through an exposure mask having L / S = 30 μm. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate R6 with a retardation film.

[Example 7]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 200 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays through an exposure mask having L / S = 30 μm. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate R7 with a retardation film.

[Example 8]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 400 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays through an exposure mask having L / S = 30 μm. After two UV exposures, the substrate R8 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes.

[Comparative Example 1]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. ^{Next, the coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm 2} (in terms of 313 nm) through an exposure mask having L / S = 20 μm. After exposure to polarized ultraviolet rays, the substrate S1 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes.

Table 1 summarizes the exposure steps of Examples 1 to 8 and Comparative Example 1 described above. In Examples 1, 2, 4 to 8, the portion covered by the exposure mask is a highly anisotropic region (hereinafter, also referred to as an anisotropic phase region), and the portion not covered by the exposure mask is low. It became an anisotropic region (hereinafter also referred to as an isotropic region). In Example 3, the region covered by the exposure mask became isotropic.

[Preparation of HAZE evaluation board]
[Preparation of substrate T1]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (in terms of 313 nm). After exposure to ultraviolet rays, the substrate T1 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes. The substrate T1 is a substrate that imitates HAZE in the anisotropic phase region of Examples 1, 2, Examples 4 to 8, and Comparative Example 1.

[Preparation of substrate T2]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with total light ultraviolet rays at 10 mJ / cm ² (313 nm conversion) and then with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). After two UV exposures, the substrate T2 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes. The substrate T2 is a substrate that imitates HAZE in the anisotropic phase region of Example 3.

[Preparation of substrate T3]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion) and then with total light ultraviolet rays at 100 mJ / cm ² (313 nm conversion). After two ultraviolet exposures, the substrate S3 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes. The substrate T3 is a substrate that imitates HAZE in the isotropic region of Example 1.

[Preparation of substrate T4]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with 100 mJ / cm ² (313 nm conversion) of total light ultraviolet rays, and then 20 mJ / cm ² (313 nm conversion) with polarized ultraviolet rays. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T4 with a retardation film. The substrate T4 is a substrate that imitates HAZE in the isotropic region of Example 2.

[Preparation of substrate T5]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Next, the coating film surface was irradiated with total light ultraviolet rays at 10 mJ / cm ² (313 nm conversion). After exposure to ultraviolet rays, it was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T5 with a retardation film. The substrate T5 is a substrate that imitates HAZE in the isotropic region of Example 3.

[Preparation of substrate T6]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 20 mJ / cm 2} (313 nm conversion) so as to be perpendicular to the polarization axis of the first polarized ultraviolet rays. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T6 with a retardation film. The substrate T6 is a substrate that imitates HAZE in the isotropic region of Examples 4 and 5.

[Preparation of substrate T7]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 100 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T7 with a retardation film. The substrate T7 is a substrate that imitates HAZE in the isotropic region of Example 6.

[Preparation of substrate T8]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 200 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After two ultraviolet exposures, the substrate T8 with a retardation film was obtained by heating on a hot plate at 140 ° C. for 20 minutes. The substrate T8 is a substrate that imitates HAZE in the isotropic region of Example 7.

[Preparation of substrate T9]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. The coated surface was irradiated with polarized ultraviolet rays at 20 mJ / cm ² (313 nm conversion). ^{Subsequently, polarized ultraviolet rays were irradiated at 400 mJ / cm 2} (313 nm conversion) so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After two UV exposures, the mixture was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T9 with a retardation film. The substrate T9 is a substrate that imitates HAZE in the isotropic region of Example 8.

[Preparation of substrate T10]
The polymer solution Q1 was filtered through a filter having a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 240 seconds to form a retardation film having a film thickness of 3.0 μm. .. Then, it was heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate T10 with a retardation film. The substrate T10 is a substrate that imitates HAZE in the isotropic region of Comparative Example 1.

[Phase difference evaluation]
Using an Axo Step manufactured by Axo Metalix, the retardation values of the substrates R1 to R8 with a retardation film and the substrate S1 with a retardation film at 550 nm were evaluated. The results are shown in Table 2.

[HAZE evaluation]
HAZE of substrates T1 to T10 with a retardation film was evaluated using HAZE Meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 2.

From the results in Table 2, from the comparison between Examples 1 to 8 and Comparative Example 1, the result that the HAZE value in the isotropic region was suppressed by irradiating the isotropic region with ultraviolet rays was obtained. However, due to the difference in the irradiation process, the retardation values of the anisotropic and isotropic phases of Examples 1 to 8 were different. Among them, in Examples 4 and 5, in addition to suppressing the HAZE value, the difference between the anisotropic phase and the isotropic phase is large, and the anisotropic phase expresses a high retardation value, and the isotropic phase position. Very good results were obtained with suppressed phase difference values. Further, from Examples 6 to 8, the result that the phase difference value of the isotropic phase was suppressed with the increase of the polarization exposure amount for the second time was obtained. This is because the methacrylate polymer powder P1 has a property of reducing the orientation at an exposure amount exceeding the optimum exposure amount.

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

Claims (7)

1. (I) A liquid crystal polymer having a property that the orientation increases as the exposure amount increases when the exposure amount is less than the optimum exposure amount, and the orientation decreases as the exposure amount increases when the exposure amount exceeds the optimum exposure amount. A step of applying a polymer composition containing a polymer having the above on a substrate to form a coating film;
   (II) In the highly anisotropic region having high optical anisotropy by irradiating the coating film obtained in step (I) with polarized ultraviolet rays, and in the region where the amount of ultraviolet rays is less than the optimum exposure amount. Through the mask at least once so that a low anisotropy region having a relatively low optical anisotropy occurs due to a shortage and an excess in the region exceeding the optimum exposure amount. Patterning also includes a step of irradiating the ultraviolet rays twice with polarized ultraviolet rays at least once; and a step of heating the coating film obtained in the steps (III) and (II) to obtain a retardation material. A method for manufacturing a single-layer retardation material.
2. The polymer composition
   (A) A side chain polymer having a side chain having a photoreactive site represented by the following formula (a);
   The method for producing a patterned single-layer retardation material according to claim 1, which comprises (B) a silane coupling agent; and (C) an organic solvent.
   

   

   (Wherein, R ¹ is an alkylene group having 1 to 30 carbon atoms, one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Also, in R ¹ of -CH ₂ CH ₂ - is, may be substituted by -CH = CH-, -CH in R ¹ ₂ - is, -O -, - NH-C (= O) -, - C (= From O) -NH-, -C (= O) -O-, -OC (= O)-, -NH-, -NH-C (= O) -NH- and -C (= O)- It may be substituted with a group selected from the group consisting of: however, the adjacent -CH _2- dos not be substituted with these groups at the same time, and -CH _2- is the terminal-in ^{R 1.} It may be _{CH 2-.}
   R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
   R ³ is a single bond, -O-, -C (= O) -O-, -OC (= 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 c ≧. When 2, each R may be the same as or different from each other.
   a is 0, 1 or 2.
   b is 0 or 1.
   c is an integer satisfying 0 ≦ c ≦ 2b + 4.
   The dashed line is the bond. )
3. The method for producing a patterned single-layer retardation material according to claim 2, wherein the side chain having the photoreactive site is represented by the following formula (a1).
   

   

   (In the formula, R ¹ , R ² and a are the same as above.
   R ^3A is a single bond, -O-, -C (= O) -O- or -OC (= O)-.
   The benzene ring in the formula (a1) includes 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 the like. It may be substituted with a substituent selected from nitro groups.
   The dashed line is the bond. )
4. (A) The method for producing a patterned single-layer retardation material according to claim 2 or 3, wherein the side chain polymer further has a side chain that expresses only liquid crystallinity.
5. The method for producing a patterned single-layer retardation material according to claim 4, wherein the side chain expressing only the liquid crystal property is a liquid crystal side chain represented by any of the following formulas (1) to (13).
   

   

   

   (In the equation, A ¹ and A ² are independent, single bond, -O-, -CH _2- , -C (= O) -O-, -OC (= O)-, -C (= O) -NH-, -NH-C (= O)-, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-.
   R ¹¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and carbon. It is an alkyl group having a number of 1 to 12 or an alkyloxy group having a carbon number of 1 to 12.
   R ¹² is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these groups. The group selected from the above, and the hydrogen atom bonded to these _{may be substituted with -NO 2} , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
   R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing complex. It is a ring group, a monovalent 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 -OC (= O)-.
   d is an integer from 1 to 12.
   k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more.
   k6 and k7 are independently integers of 0 to 2, but the total of k6 and k7 is 1 or more.
   m1, m2 and m3 are independently integers of 1 to 3.
   n is 0 or 1.
   Z ¹ and Z ² are independently single-bonded, -C (= O)-, -CH ₂ O-, -CH = N- or -CF _2- .
   The dashed line is the bond. )
6. The method for producing a patterned single-layer retardation material according to claim 5, wherein the side chain that expresses only the liquid crystal property is a liquid crystal side chain represented by any of the formulas (1) to (11).
7. A single-layer retardation material manufactured by the method according to any one of claims 1 to 6.