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

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

Fabrication method of patterned monolayer retardation material

technical field

The present invention relates to a manufacturing method of a patterned monolayer retardation material and a monolayer retardation material. In detail, the present invention relates to a patterned monolayer retardation material obtained from a composition comprising a liquid crystalline polymer, wherein the liquid crystalline polymer has: exposure at an exposure amount lower than an optimum exposure amount The higher the amount, the higher the orientation, and the lower the orientation at a higher exposure than the optimum exposure, the above-mentioned liquid crystalline polymers can be preferably used for display devices, recording materials, etc. In particular, the material having optical properties can be preferably used for optical compensation films such as polarizing plates for liquid crystal displays and retardation plates.

Background technique

In accordance with demands for improved display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films that control the molecular alignment structure inside as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, films obtained by utilizing the optical anisotropy possessed by polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compound used here is usually a liquid crystal compound having a polymerizable group and a liquid crystal structure moiety (a structure site having a spacer portion and a mesogen portion), and an acryl group is widely used as the polymerizable group.

The polymerizable liquid crystal compound described above is usually prepared as a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays. For example, there is known a method in which a polymer is obtained by supporting a specific polymerizable liquid crystal compound having an acryl group between supports obtained by performing an alignment treatment, and irradiating the compound with radiation while maintaining the compound in a liquid crystal state (Patent Document 1). A method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two types of polymerizable liquid crystal compounds having acryl groups or a composition in which a chiral liquid crystal is mixed with the mixture and irradiating ultraviolet rays (Patent Document 2).

In addition, polymerizable liquid crystal compounds that do not require a liquid crystal aligning film, alignment films using polymers (Patent Documents 3 and 4), and alignment films using polymers containing photocrosslinking sites (Patent Documents 5 and 6) are each reported. A variety of single-layer coating type alignment films.

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

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 62-70407

Patent Document 2: Japanese Patent Application Laid-Open No. 9-208957

Patent Document 3: Specification of 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 Patent Laid-Open No. 11-189665

SUMMARY OF THE INVENTION

The problem to be solved by the invention

The present invention has been made in view of the above-mentioned problems, and its object is to provide a simple process that exhibits a high phase difference value in the anisotropic phase, suppresses the phase difference value of the isotropic phase, and further suppresses turbidity (HAZE ) patterned monolayer retardation material manufacturing method.

means of solving problems

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have found that by using a composition containing a specific polymer and a specific additive, and applying the following method for producing a patterned retardation material, it is possible to produce a phase difference material in an anisotropic phase. A patterned monolayer retardation material that exhibits a high retardation value, suppresses the retardation value of an isotropic phase, and further suppresses haze (HAZE), thereby completing the present invention.

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

1. A method for manufacturing a patterned monolayer retardation material, comprising:

(I) The step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer on a substrate, wherein the liquid crystalline polymer has a higher exposure dose than an optimal exposure dose Then the orientation increases, and the more exposure is higher than the optimal exposure, the orientation decreases;

(II) A step of irradiating the coating film obtained in the step (I) with ultraviolet rays twice to generate a high anisotropy region and a low anisotropy region, wherein the irradiation is performed at least once through a mask, and at least once Irradiation is performed using polarized ultraviolet rays, the above-mentioned high anisotropy region has high optical anisotropy by irradiating polarized ultraviolet rays, and the above-mentioned low anisotropy region is made by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount, and in a high Excessive in areas of optimal exposure with relatively low optical anisotropy; and

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

2. The method for producing a patterned monolayer retardation material according to 1, wherein,

The above 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) organic solvent;

[Chemical formula 1]

In the formula, R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the above-mentioned alkylene group are or are not substituted by fluorine atoms or organic groups; in addition, -CH in R ¹ ₂ CH ₂ - is or is not substituted by -CH=CH-, -CH ₂ - in R ¹ is or is not selected from -O-, -NH-C(=O)-, -C(=O)- Group substitution in NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)-; Wherein, the adjacent -CH ₂ - will not be substituted by these groups at the same time; in addition, -CH ₂ - is or is not the terminal -CH ₂ - in R ¹ ;

R ² is a bivalent aromatic group, a bivalent alicyclic group, a bivalent heterocyclic group or a bivalent condensed cyclic 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, When c≥2, each R is the same 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 dotted line is the bonding site.

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

[Chemical formula 2]

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 formula (a1) is or is not selected from 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, and an alkyl group having 1 to 6 carbon atoms. Substituent substitution in haloalkoxy, cyano and nitro of 6;

The dotted line is the bonding site.

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

5. The method for producing a patterned monolayer retardation material according to 4, wherein the side chain that only exhibits liquid crystallinity is a liquid crystallinity side chain represented by any one of the following formulae (1) to (13);

[Chemical formula 3]

[Chemical formula 4]

In formulas (1) to (13), A ¹ and A ² are each independently a 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, biphenyl group, furyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon atom an alkyl group of 1 to 12 or an alkoxy of 1 to 12 carbon atoms;

R ¹² is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a combination thereof Groups whose hydrogen atoms are or are not substituted by -NO ₂ , -CN, halogen atoms, alkyl groups with 1 to 5 carbon atoms or alkoxy groups with 1 to 5 carbon atoms;

R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing hetero group A ring group, a monovalent alicyclic hydrocarbon group with 5 to 8 carbon atoms, an alkyl group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms;

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

d is an integer from 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 sum of k6 and k7 is 1 or more;

m1, m2 and m3 are each independently an integer from 1 to 3;

n is 0 or 1;

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

The dotted line is the bonding site.

6. The method for producing a patterned monolayer retardation material according to 5, wherein the side chain that only exhibits liquid crystallinity is a liquid crystallinity side chain represented by any one of formulae (1) to (11).

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

effect of invention

According to the present invention, it is possible to provide a patterned retardation material capable of suppressing whitening of the film in the region with a low retardation value while having a region with a high retardation value and a region with a low retardation value.

Detailed ways

The manufacturing method of the patterned single-layer retardation material of the present invention includes the following steps [I] to [III]:

(I) The step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer on a substrate, wherein the liquid crystalline polymer has a higher exposure dose than an optimal exposure dose Then the orientation increases, and the more exposure is higher than the optimal exposure, the orientation decreases;

(II) A step of irradiating the coating film obtained in the step (I) with ultraviolet rays twice to generate a high anisotropy region and a low anisotropy region, wherein the irradiation is performed at least once through a mask, and at least once Irradiation is performed using polarized ultraviolet rays, the above-mentioned high anisotropy region has high optical anisotropy by irradiating polarized ultraviolet rays, and the above-mentioned low anisotropy region is made by making the amount of ultraviolet rays insufficient in a region lower than the optimum exposure amount, and in a high Excessive in areas of optimal exposure with relatively low optical anisotropy; and

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

The above-mentioned polymer composition comprises a liquid crystalline polymer, which has an increased orientation at an exposure level lower than the optimum exposure level, and orientation at a higher exposure level than the optimum exposure level. The property of decreasing property (hereinafter, also simply referred to as a side chain type polymer), the coating film obtained by using the above-mentioned polymer composition is a film containing a photosensitive side chain type polymer capable of expressing liquid crystallinity. This coating film was not subjected to rubbing treatment, and was subjected to orientation treatment by polarized irradiation. Moreover, after polarizing irradiation, the process of heating the said coating film is carried out, and the film (henceforth, also called a single-layer retardation material) which provides optical anisotropy is formed. At this time, the slight anisotropy expressed by polarized irradiation forms a driving force, and the liquid crystalline side chain polymer itself is effectively reoriented by self-organization. As a result, efficient alignment treatment is realized, and a single-layer retardation material imparting high optical anisotropy can be obtained.

Further, the method for producing a patterned single-layer retardation material of the present invention has the step of using polarized ultraviolet rays at least once through a mask so as to generate a high anisotropy region and a low anisotropy region at least once. , the step of irradiating ultraviolet rays twice, wherein the high anisotropy region has high optical anisotropy by irradiating polarized ultraviolet rays, and the low anisotropy region is made by making the amount of ultraviolet rays insufficient in the region below the optimum exposure amount , and excess in regions above the optimum exposure with relatively low optical anisotropy. By having the above-mentioned steps, the hardness of the film is increased by irradiating ultraviolet rays both in the region having anisotropy and in the region where the anisotropy is reduced, and as a result, in the patterned retardation material, the anisotropy can be suppressed. The clouding of the film in the region with low heterogeneity, that is, the so-called whitening phenomenon. Thereby, a patterned retardation material in which HAZE is suppressed 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 contains (A) a side chain type 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) Component is a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and is a side chain (hereinafter, also referred to as a side chain) having a photoreactive site represented by the following formula (a). a) side chain type polymer.

[Chemical formula 5]

In formula (a), R ¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. In addition, -CH ₂ CH ₂ - in R ¹ may be substituted by -CH=CH-, and -CH ₂ - in R ¹ may be selected from -O-, -NH-C(=O)-, -C( of =O)-NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- group substitution. Among them, the adjacent -CH ₂ - will not be substituted by these groups at the same time. In addition, -CH ₂ - may be -CH ₂ - at the terminal in R ¹ . R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic 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, When c≥2, each R may be the same or different from each other. a is 0, 1 or 2. b is 0 or 1. c is an integer satisfying 0≤c≤2b+4. The dotted line is the bonding site.

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

As a divalent aromatic group represented by R< ² >, a phenylene group, a biphenylene group, etc. are mentioned. A cyclohexanediyl group etc. are mentioned as a divalent alicyclic group represented by R< ² >. Furandiyl etc. are mentioned as a divalent heterocyclic group represented by R< ² >. As a divalent condensed cyclic group represented by R ² , a naphthylene group etc. are mentioned.

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

[Chemical formula 6]

In formula (a1), R ¹ , R ² and a are the same as described above. R ^3A is a single bond, -O-, -C(=O)-O- or -OC(=O)-. The benzene ring in the formula (a1) may be 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, and an alkyl group having 1 to 6 carbon atoms. Substituents in haloalkoxy, cyano and nitro are substituted. The dotted line is the bonding site.

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

[Chemical formula 7]

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

(A) It is preferable that a side chain type polymer reacts under the light of the wavelength range of 250-400 nm, and shows liquid crystallinity in the temperature range of 100-300 degreeC. The (A) 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 a crosslinking reaction or an isomerization reaction can be induced in response to light. The structure of the photosensitive side chain type polymer that can express liquid crystallinity is not particularly limited as long as it satisfies the above-mentioned properties, but it is preferable to have a rigid mesogen component in the side chain structure. When the above-mentioned side chain type polymer is used as a single-layer retardation material, stable optical anisotropy can be obtained.

As a more specific example of the structure of the photosensitive side-chain type polymer capable of expressing liquid crystallinity, it is preferable to have a structure selected from the group consisting of (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radically polymerizable groups such as the main chain and at least one of siloxane constitute the main chain, and the side The structure of chain a.

Moreover, since (A) side chain type polymer shows liquid crystallinity in the temperature range of 100-300 degreeC, it is more preferable to have a side chain (henceforth, also referred to as a side chain b) which shows only liquid crystallinity. It should be noted that "only expressing liquid crystallinity" here means that the polymer having only the side chain b does not occur in the production process of the retardation material of the present invention (that is, the steps (I) to (III) to be described later). Shows photosensitivity and only exhibits liquid crystallinity.

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

[Chemical formula 8]

[Chemical formula 9]

In formulas (1) to (13), A ¹ and A ² are each independently a 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, biphenyl group, furyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon atom An alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. R ¹² is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a combination thereof Groups, and the hydrogen atoms bonded to them may be substituted with -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ¹³ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing hetero group 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 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 sum of k6 and k7 is 1 or more. m1, m2, and m3 are each independently an integer of 1 to 3. n is 0 or 1. Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ O-, -CH=N- or -CF ₂ -. The dotted line is the bonding site.

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

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

As a monomer (henceforth, also called monomer M1) which has the structure represented by Formula (a), the compound represented by following formula (M1) is mentioned.

[Chemical formula 10]

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

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

[Chemical formula 11]

(wherein, R ¹ , R ² , R ^3A , R 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]

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

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

[Chemical formula 13]

In formulas (PL-1) to (PL-5), Q ¹ , Q ² and Q ³ are hydrogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, or those obtained by substitution with halogen A linear or branched alkyl group having 1 to 10 carbon atoms. The dotted line is the bonding site with R ¹ or L. Among the above-mentioned monomers, some 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 formulae (M1-1) to (M1-5).

[Chemical formula 14]

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

A monomer having a structure that exhibits only liquid crystallinity (hereinafter, also referred to as monomer M2) is a monomer derived from a polymer that exhibits liquid crystallinity and can form a mesogen group at a side chain site. body.

The mesogen group in the side chain may be a group that independently forms a mesogen structure, such as biphenyl and phenyl benzoate, or a mesogen structure such as benzoic acid, where side chains are hydrogen-bonded to each other. the group. As the mesogen group which the side chain has, the following structures are preferable.

[Chemical formula 15]

As a more specific example of the monomer M2, it is preferable to have: derived from hydrocarbons, (meth)acrylates, itaconate, fumarate, maleate, α-methylene-γ- Radical polymerizable groups such as butyrolactone, styrene, vinyl, maleimide, norbornene, and the like, and at least one polymerizable group of siloxane, and a polymerizable group represented by formulas (1) to (13) ) is a structure composed of at least one of ). The monomer M2 is particularly preferably a monomer having a (meth)acrylate as a polymerizable group, and preferably a monomer whose side chain terminal is -COOH.

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

[Chemical formula 16]

[Chemical formula 17]

(where, PL and p are the same as above)

In addition, other monomers may be copolymerized within a range that does not impair the expressive ability of photoreactivity and/or liquid crystallinity. Examples of other monomers include commercially available monomers capable of radical polymerization. Specific examples of other monomers 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, fumaric acid, and the like.

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

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl methacrylate, and methyl methacrylate. Anthracene methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid -2-methoxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxymethacrylate Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, methyl methacrylate 8-ethyl-8-tricyclodecyl acrylate, etc.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example. As a styrene compound, styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, etc. are mentioned, for example. As a maleimide compound, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned, for example.

From the viewpoint of photoreactivity, the content of the side chain a in the side chain type polymer of the present invention is preferably 20 to 99.9 mol %, more preferably 30 to 95 mol %, and further preferably 40 to 90 mol %.

From the viewpoint of retardation value, the content of the side chain b in the side chain type 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 %.

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

(A) The manufacturing method of the side chain type polymer of a component is not specifically limited, Industrial general methods can be utilized. Specifically, it can be produced by radical polymerization, cationic polymerization, or anionic polymerization of vinyl groups using the above-mentioned monomer M1, monomer M2, and other monomers as desired. Among them, radical polymerization is particularly preferred from the viewpoint of ease of reaction control and the like.

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

The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of the above-mentioned radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, Benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, di-tert-butyl peroxide, Cumyl peroxide, dilauroyl peroxide, etc.), peroxyacetals (dibutylperoxycyclohexane, etc.), peroxyalkyl esters (tert-butyl peroxyneodecanoate, peroxyneodecanoate, etc.) tert-butyl oxypivalate, tert-amyl peroxy-2-ethylcyclohexane acid, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (even azobisisobutyronitrile and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). A radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types.

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, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. Xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropyl Propiophenone, 1-Hydroxycyclohexyl phenyl ketone, Isopropylbenzoin ether, Isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy- 2-Phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4, 4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxybenzene vinyl)-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)-same Triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 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'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene) base)-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 '-Bimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecyl Alkylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1- base)-phenyl)titanium, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-hexyl) ylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl) Carbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl)bis Benzophenone, 2-(3-Methyl-3H-benzothiazole-2-ylidene)-1-naphthalen-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazole -2(3H)-ylidene)-1-(2-benzoyl)ethanone and the like. A radical photopolymerization initiator may be used individually by 1 type, and may be used in mixture of 2 or more types.

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

The organic solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced polymer. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl -ε-caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, γ-butyrolactone, isopropanol, methoxymethyl pentanol, dipentane alkene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monoacetate Butyl 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 ether Ethyl-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, methyl pyruvate, pyruvic acid ethyl ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 -propyl 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, etc.

The above-mentioned organic solvents may be used alone or in combination of two or more. Moreover, even if it is a solvent which does not melt|dissolve the produced polymer, you may mix and use with the said organic solvent in the range in which the produced polymer does not precipitate. In addition, in the radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

The polymerization temperature at the time of radical polymerization can select the arbitrary temperature of 30-150 degreeC, Preferably it is the range of 50-100 degreeC. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it will be difficult to obtain a polymer with a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid will become too high and uniform stirring will become difficult. Therefore, the monomer concentration Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction can be carried out at a high concentration at the beginning of the reaction, and then the organic solvent can be added.

In the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer decreases, and if the ratio of the radical polymerization initiator to the monomer is small, the obtained high molecular weight Since the molecular weight of the molecule increases, the ratio of the radical initiator is preferably 0.1 to 10 mol % with respect to the polymerized monomer. In addition, various monomer components, solvents, initiators, etc. may be added during the polymerization.

When recovering the produced polymer from the reaction solution obtained by the above-mentioned reaction, the reaction solution may be poured into a poor solvent to precipitate the above-mentioned polymer. Examples of poor solvents 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. Wait. After the polymer deposited in the poor solvent is recovered by filtration, it can be dried at normal temperature or by heating under normal pressure or reduced pressure. In addition, if the operation of re-dissolving the recovered polymer in an organic solvent and reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more types of poor solvents selected from these, since the efficiency of purification is further improved.

The weight-average molecular weight of the (A) side chain type polymer of the present invention measured by GPC (Gel Permeation Chromatography) method is obtained in consideration of the strength of the obtained coating film, the workability at the time of coating film formation, and the uniformity of the coating film. Preferably it is 2000-2000000, More preferably, it is 2000-1000000, More preferably, it is 5000-200000.

[(B) Silane Coupling Agent]

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

[Chemical formula 18]

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

Examples of the reactive functional group represented by R ²¹ include an amino group, a urea group, a (meth)acryloyloxy group, a vinyl group, an epoxy group, a mercapto group, a group having an oxetane structure, and the like, and an amino group is preferred , urea group, (meth)acryloyloxy group and groups with oxetane structure, etc. Particularly preferred 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. As said halogen atom, a chlorine atom, a bromine atom, etc. are mentioned. The alkoxy group having 1 to 3 carbon atoms is preferably a linear or branched group, and specifically, a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group. In addition, specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group. .

Specific examples of the (B) silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropylmethylsilane. Dimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloyloxypropyl Trimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxysilane Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-(3-ethyloxetane -3-ylmethoxy)propyltrimethoxysilane, 3-(3-ethyloxetan-3-ylmethoxy)propyltriethoxysilane, 3-(3-ethyl Oxetan-3-ylmethoxy)propylmethyldimethoxysilane, 3-(3-ethyloxetan-3-ylmethoxy)propylmethyldiethoxy Silane etc.

Among them, 3-(3-ethyloxetan-3-ylmethoxy)propyltrimethoxysilane, 3-(3-ethyloxetan-3-ylmethoxy) ) propyltriethoxysilane, 3-(3-ethyloxetan-3-ylmethoxy)propylmethyldimethoxysilane, 3-(3-ethyloxetane Alk-3-ylmethoxy)propylmethyldiethoxysilane and the like. As said silane coupling agent, a commercial item can be used.

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

[(C) Organic solvent]

The organic solvent of the component (C) is not particularly limited as long as it 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, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, γ-butyrolactone, 3 -Methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3 - Dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate , Diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, etc. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

[other ingredients]

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

Specific examples of the solvent (poor solvent) for improving the uniformity and surface smoothness of the film thickness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. agent, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoethyl Ester, 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 Alcohol 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 acetate Isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane , n-octane, ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, pyruvic acid methyl ester, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionate Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy Ethyl-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate , 2-(2-ethoxypropoxy) propanol and other solvents with low surface tension, etc.

The said poor solvent may be used individually by 1 type, and may be used in mixture of 2 or more types. When the above-mentioned poor solvent is used, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition, the content thereof is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass in the solvent.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned. More specifically, for example, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products), MEGAFAC (registered trademark) F171, F173, R-30, R-40 (manufactured by DIC Corporation), FLUORAD FC430, FC431 (manufactured by 3M Corporation), AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMICHEMICAL Corporation) and the like. The content of the surfactant is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (A) component.

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

Specific examples of the phenolic plastic additive are shown below, but are 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, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylcarbamate base) cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When using the compound which improves the adhesiveness with a board|substrate, 0.1-30 mass parts are preferable with respect to 100 mass parts of polymer components contained in a polymer composition, and 1-20 mass parts are more preferable. When content is less than 0.1 mass part, the effect of improving adhesiveness cannot be anticipated, and when it exceeds 30 mass parts, the orientation of a liquid crystal may deteriorate.

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

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin ketone, carbonyl group Dicoumarins, aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, Xanthone, thioxanthone, benzoanthrone, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3 -Methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methyl Benzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenylmethylene)-3-methyl-β- Naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl- β-Naphthoxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzo oxazoline, 2-(4-biphenylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxaline oxazoline, 2-(4-biphenylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthalene oxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthene, etc.), 2-[( m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethyl ketone, etc. ), naphthalene (2-naphthalene methanol, 2-naphthoic acid, etc.), anthracene (9-anthracene methanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merlotcoumarin, etc. Among them, aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin ketone, carbonyl dicoumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone acetal are preferred ketone.

In the polymer composition of the present invention, in addition to the above-mentioned substances, in order to change the electrical properties such as the dielectric constant and conductivity of the retardation material, in the range that does not impair the effect of the present invention, a dielectric and a conductive substance may be added, and further, In order to increase the hardness and density of the film when used as a retardation material, a crosslinkable compound may be added.

[Preparation of polymer composition]

The polymer composition of the present invention is preferably prepared as a coating liquid in a manner suitable for forming a single-layer retardation material. That is, the polymer composition used in the present invention is preferably prepared as components (A) and (B), as well as the above-mentioned solvent or compound for improving the uniformity of film thickness and surface smoothness, and for improving the adhesion between the liquid crystal aligning film and the substrate A solution obtained by dissolving the compound and the like in the organic solvent of the component (C). Here, it is preferable that content of (A) component is 1-30 mass % in the composition of this invention.

In addition to the polymer of (A) component, the polymer composition of this invention may contain another polymer in the range which does not impair liquid crystal expression ability and photosensitivity ability. In this case, the content of other polymers in the polymer component is preferably 0.5 to 80% by mass, and more preferably 1 to 50% by mass. Examples of other polymers include polymers such as poly(meth)acrylates, polyamic acids, and polyimides that are not photosensitive side-chain polymers that can express 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) The step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer on a substrate, wherein the liquid crystalline polymer has a higher exposure dose than an optimal exposure dose Then the orientation increases, and the more exposure is higher than the optimal exposure, the orientation decreases;

(II) A step of irradiating the coating film obtained in the step (I) with ultraviolet rays twice to generate a high anisotropy region and a low anisotropy region, wherein the irradiation is performed at least once through a mask, and at least once The irradiation is performed using polarized ultraviolet rays, the above-mentioned high anisotropy region has high optical anisotropy by irradiating polarized ultraviolet rays, and the above-mentioned low anisotropy region is made by making the amount of ultraviolet light insufficient in the region below the optimum exposure amount, and in the high Excessive in areas of optimal exposure with relatively low optical anisotropy; and

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

[Process (I)]

(I) is a step of forming a coating film by applying a polymer composition containing a liquid crystalline polymer on a substrate, wherein the liquid crystalline polymer has a higher exposure dose than an optimal exposure dose. There is a property that the orientation increases in many cases, and the orientation decreases as the exposure amount increases at an exposure amount higher than the optimum exposure amount. More specifically, the composition is applied to a substrate (e.g., by means of bar coating, spin coating, flow coating, roll coating, slot coating, spin coating followed by slot coating, ink jet method, printing method, and the like). , silicon/silicon dioxide covered substrates, silicon nitride substrates, substrates covered with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates, etc.), membranes (eg, triacetyl cellulose (TAC) ) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film and other resin films) and the like. After coating, a coating film can be obtained by evaporating the solvent at preferably 50 to 200°C, more preferably 50 to 150°C, by heating means such as a hot plate, thermal cycle oven, or IR (infrared) oven.

[Process (II)]

In the step (II), the coating film obtained in the step (I) is irradiated with ultraviolet rays twice to generate a high anisotropy region and a low anisotropy region, wherein the irradiation is performed at least once through a mask, Irradiate with polarized ultraviolet light at least once, the high anisotropy region has high optical anisotropy by irradiating polarized ultraviolet light, and the low anisotropy region is caused by making the amount of ultraviolet light insufficient in the region below the optimum exposure amount, and excess in regions above the optimum exposure with relatively low optical anisotropy. As a more specific form of the said process, the following process (II-1) - process (II-3) are mentioned.

[Process (II-1)]

In the step (II-1), the first ultraviolet irradiation is performed through a mask so as to cover only the region where anisotropy is to be imparted. 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. In this way, anisotropy is imparted to the portion covered by the mask during the first irradiation by only irradiating the polarized ultraviolet rays once, and the second ultraviolet irradiation is performed on the region subjected to the first ultraviolet irradiation, so that each Anisotropy decreases.

[Process (II-2)]

Step (II-2) After the first ultraviolet irradiation using polarized ultraviolet rays, the second ultraviolet irradiation is performed through a mask so as to cover only the region where anisotropy is to be imparted. The ultraviolet rays in the second irradiation may be full-spectrum ultraviolet rays or polarized ultraviolet rays. Thereby, anisotropy is imparted to the portion covered by the mask at the time of the second irradiation by only irradiating the polarized ultraviolet light once, and the anisotropy is reduced in the region subjected to the second ultraviolet irradiation.

[Process (II-3)]

Step (II-3) After the first ultraviolet irradiation using plenoptic ultraviolet rays, the second polarization ultraviolet irradiation is performed through a mask so as to cover only the region where anisotropy is not intended to be imparted. It is preferable that the irradiation amount of the total light ultraviolet rays at the time of the 1st irradiation is less than the irradiation amount of the 2nd polarized ultraviolet rays. As a result, anisotropy is imparted to the portion not covered by the mask during the second irradiation by irradiating the polarized ultraviolet rays, and anisotropy is suppressed only in the region irradiated with the first ultraviolet ray.

In addition, when irradiating polarized ultraviolet rays, polarized ultraviolet rays are irradiated to the board|substrate through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength of 100 to 400 nm can be used. It is preferable to select an optimal wavelength through a filter etc. according to the kind of coating film used. In addition, for example, ultraviolet rays having a wavelength of 290 to 400 nm can be selectively used so that a 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 preferably set to achieve the maximum value of ΔA (hereinafter, also referred to as ΔAmax) of the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the perpendicular direction in the coating film. It is within the range of 1 to 70% of the amount, and more preferably within the range of 1 to 50%.

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

[Process (III)]

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

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

The heating temperature is preferably within the range of the temperature at which the polymer contained in the polymer composition expresses liquid crystallinity (hereinafter, referred to as liquid crystal expression temperature). In the case of the surface of a thin film such as a coating film, it is expected that the liquid crystal expression temperature of the coating film surface is 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 temperature of the liquid crystal on the surface of the coating film. That is, the range of the heating temperature after polarized ultraviolet irradiation is preferably set to a temperature lower than the lower limit of the range of the liquid crystal expression temperature of the polymer used by 10°C as the lower limit and lower than the upper limit of the liquid crystal temperature range by 10°C The temperature is the upper limit of the temperature range. If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy of the coating film by heat tends to be insufficient, and if the heating temperature is too high compared to the above temperature range, the coating film may The state tends to be close to the isotropic liquid state (isotropic phase), and in this case, it may become difficult to reorient in one direction by self-organization.

It should be noted that the liquid crystal expression temperature refers to the liquid crystal transition temperature or higher at which the polymer or coating film surface undergoes phase transition from the solid phase to the liquid crystal phase, and the isotropic phase transition at which the phase transition occurs from the liquid crystal phase to the isotropic phase. The temperature below the temperature (Tiso). For example, to express liquid crystallinity at 130°C or lower means that the liquid crystal transition temperature at which 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, optical properties, and electrical properties of the substrate to be used, and, for example, is preferably 0.5 to 10 μm.

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

Example

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

M1 as a monomer having a photoreactive group and M2 as a monomer having a liquid crystal group used in the examples are shown below. Each of M1 and M2 was synthesized as shown below. M1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. M2 was synthesized according to the synthesis method described in Japanese Patent Laid-Open No. 9-118717. In addition, the side chain derived from M1 exhibits photoreactivity and liquid crystallinity, and the side chain derived from M2 has only liquid crystallinity.

[Chemical formula 20]

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

(Organic solvents)

THF: Tetrahydrofuran

NMP: N-ethyl-2-pyrrolidone

BCS: Butyl Cellosolve

PGME: Propylene Glycol Monomethyl Ether

(polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

(polymerization initiator)

(additive)

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

[Chemical formula 21]

[Synthesis 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), and after degassing by a diaphragm pump, AIBN (1.23 g: 7.5 mmol) was added, and degassing was performed again. Then, it was made to react at 60 degreeC for 8 hours, and the polymer solution of methacrylate was obtained. The polymer solution was added dropwise to a mixed solution of methanol (3020 g) and pure water (1200 g), and the resulting precipitate was filtered. 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 stirred and dissolved at room temperature for 3 hours. To this solution, PGME (10.0 g), BCS (20.0 g), TESOX-D (1.00 g) and MEGAFACE R-40 (0.01 g) were added and stirred to obtain a polymer solution Q1.

[Fabrication of the retardation value evaluation substrate]

[Example 1]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 20 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays were irradiated to the coating film surface, and then 100 mJ/cm ² (313 nm conversion) of total light ultraviolet rays were irradiated through an exposure mask having L/S=30 μm. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R1 with a retardation film.

[Example 2]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, through an exposure mask having L/S=30 μm, 100 mJ/cm ² (313 nm conversion) of total light ultraviolet rays was irradiated to the coating film surface, then the exposure mask was removed, and polarized ultraviolet rays 20 mJ/cm ² (313 nm conversion) were irradiated. . After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R2 with a retardation film.

[Example 3]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 10 mJ/cm ^{2 (equivalent to 313 nm) of total light ultraviolet rays were irradiated to the coating film surface, and then 20 mJ/cm 2 (} equivalent to 313 nm) of polarized ultraviolet rays were irradiated through an exposure mask having L/S=30 μm. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R3 with a retardation film.

[Example 4]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, 20 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays was irradiated 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 2 times of ultraviolet exposure, it heated with the hotplate of 140 degreeC for 20 minutes, and obtained the board|substrate R4 with retardation film.

[Example 5]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion) through an exposure mask having L/S=30 μm. Next, the exposure mask was removed, and 20 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays was irradiated so as to be perpendicular to the polarization axis of the first polarized ultraviolet rays. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R5 with a retardation film.

[Example 6]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, 100 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays was irradiated 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 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R6 with a retardation film.

[Example 7]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, 200 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays was irradiated 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 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R7 with a retardation film.

[Example 8]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, 400 mJ/cm ² (313 nm conversion) of polarized ultraviolet rays was irradiated 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 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate R8 with a retardation film.

[Comparative Example 1]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, the coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion) through an exposure mask having L/S=20 μm. After polarized ultraviolet light exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate S1 with a retardation film.

If the exposure steps of the above Examples 1 to 8 and Comparative Example 1 are summarized, they are as described in Table 1. In addition, in Examples 1, 2, 4 to 8, the portion covered by the exposure mask formed a highly anisotropic region (hereinafter, also referred to as an anisotropic region), and the portion not covered by the exposure mask A low anisotropy region (hereinafter, also referred to as an isotropic phase region) is formed. In Example 3, the area covered by the exposure mask formed an isotropic phase.

[Table 1]

[Production of HAZE Evaluation Board]

[Production of substrate T1]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion) were irradiated to the coating film surface. After ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T1 with a retardation film. The substrate T1 is a substrate that simulates the HAZE of the anisotropic regions of Examples 1 and 2, Examples 4 to 8, and Comparative Example 1.

[Fabrication of substrate T2]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 10 mJ/cm ^{2 (313 nm conversion) of total light ultraviolet rays were irradiated to the coating film surface, and then 20 mJ/cm 2 (} 313 nm conversion) of polarized ultraviolet rays were irradiated. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T2 with a retardation film. The substrate T2 is a substrate that simulates the HAZE of the anisotropic region of Example 3.

[Production of substrate T3]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 20 mJ/cm ^{2 (313 nm conversion) of polarized ultraviolet rays were irradiated to the coating film surface, and then 100 mJ/cm 2 (} 313 nm conversion) of total light ultraviolet rays were irradiated. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate S3 with a retardation film. The substrate T3 is a substrate simulating the HAZE of the isotropic phase region of Example 1.

[Production of substrate T4]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 100 mJ/cm ² (313 nm conversion) of total light ultraviolet rays were irradiated to the coating film surface, and then 20 mJ/cm ² (313 nm conversion) polarized ultraviolet rays were irradiated. After 2 times of ultraviolet exposure, it heated with the hotplate of 140 degreeC for 20 minutes, and obtained the board|substrate T4 with retardation film. The substrate T4 is a substrate that simulates the HAZE of the isotropic phase region of Example 2.

[Fabrication of substrate T5]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, 10 mJ/cm ² (313 nm conversion) of total light ultraviolet rays was irradiated to the coating film surface. After ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T5 with a retardation film. The substrate T5 is a substrate that simulates the HAZE of the isotropic phase region of Example 3.

[Production of substrate T6]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion) were irradiated so as to be perpendicular to the polarization axis of the first polarized ultraviolet rays. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T6 with a retardation film. The substrate T6 is a substrate that simulates the HAZE of the isotropic phase region of Examples 4 and 5.

[Fabrication of substrate T7]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, polarized ultraviolet rays of 100 mJ/cm ² (313 nm conversion) were irradiated so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T7 with a retardation film. The substrate T7 is a substrate simulating the HAZE of the isotropic phase region of Example 6.

[Production of substrate T8]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, polarized ultraviolet rays of 200 mJ/cm ² (313 nm conversion) were irradiated so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T8 with a retardation film. The substrate T8 is a substrate simulating the HAZE of the isotropic phase region of Example 7.

[Fabrication of substrate T9]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. The coating film surface was irradiated with polarized ultraviolet rays of 20 mJ/cm ² (313 nm conversion). Next, polarized ultraviolet rays of 400 mJ/cm ² (313 nm conversion) were irradiated so as to be parallel to the polarization axis of the first polarized ultraviolet rays. After 2 times of ultraviolet exposure, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate T9 with a retardation film. The substrate T9 is a substrate that simulates the HAZE of the isotropic phase region of Example 8.

[Production of substrate T10]

The polymer solution Q1 was filtered through a filter with 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 with a thickness of 3.0 μm. Next, it heated for 20 minutes with the hotplate of 140 degreeC, and obtained the board|substrate T10 with a retardation film. The substrate T10 is a substrate that simulates the HAZE of the isotropic phase region of Comparative Example 1.

[Phase Difference Evaluation]

The retardation value at 550 nm of the substrates R1 to R8 with a retardation film and the substrate S1 with a retardation film was evaluated using Axo Step manufactured by Axo Metrix. The results are shown in Table 2.

[HAZE evaluation]

HAZE with retardation film substrates T1 to T10 was evaluated using HAZE Meter HZ-V3 manufactured by Suga Testing Machine Co., Ltd. The results are shown in Table 2.

[Table 2]

From the results in Table 2, the comparison between Examples 1 to 8 and Comparative Example 1 shows that the HAZE value of the isotropic phase region is suppressed by irradiating the isotropic phase region with ultraviolet rays. However, due to the difference in the irradiation process, the retardation values of the anisotropic phase and the isotropic phase of Examples 1 to 8 were different. Among them, in Examples 4 and 5, in addition to the suppressed HAZE value, the difference between the phase difference values of the anisotropic phase and the isotropic phase is large, and the anisotropic phase shows a high phase difference value, and the isotropic phase is obtained. Very good results in which the phase difference values are suppressed. In addition, according to Examples 6 to 8, it was found that the retardation value of the isotropic phase was suppressed as the second polarization exposure amount increased. The reason for this is that the methacrylate polymer powder P1 has a property of decreasing 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 monolayer retardation material in which the HAZE value of the isotropic phase region is suppressed.

Claims (7)

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

(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

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

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

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;

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-；

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 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 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 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);

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)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;

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 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.