KR20230079105A - Manufacturing method of single-layer retardation material - Google Patents

Abstract

(I) a step of applying a polymer composition on a substrate and drying it to form a coating film; and (II) a step of irradiating the coating film with polarized ultraviolet rays, wherein the polymer composition emits light with a wavelength of 365 nm. A monolayer containing a polymer having a photoreactive site to be quantified or photoisomerized in a side chain, and the amount of light at a wavelength of 313 nm in the total amount of light at a wavelength of 365 nm and light at a wavelength of 313 nm in polarized ultraviolet light is 10% or less According to the method for manufacturing a phase difference material, a single layer phase difference material having a high phase difference value and high birefringence can be manufactured.

Description

Manufacturing method of single-layer retardation material

The present invention relates to a method for manufacturing a single-layer retardation material, and more specifically, materials having optical properties suitable for applications such as display devices and recording materials, particularly organic electroluminescence (EL) display devices and liquid crystals. It relates to a method for producing a single-layer retardation material that can be suitably used for optical compensation films such as polarizing plates and retardation plates for displays.

Demand for a polymer film with a controlled internal molecular orientation structure as an optical compensation film such as a polarizing plate or a retardation plate is increasing due to demands for improvement in display quality and weight reduction of organic EL display devices and liquid crystal display devices. In order to meet this demand, the development of a film using the optical anisotropy of a polymerizable liquid crystal compound is being made. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural site (a structural site having a spacer portion and a mesogen portion), and an acryl group is widely used as the polymerizable group.

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

In addition, various monolayers such as alignment films using polymerizable liquid crystal compounds or polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4) and alignment films using polymers containing photocrosslinking moieties (Patent Documents 5 and 6) An application type orientation film has been reported.

Conventionally, in manufacturing a liquid crystal alignment film or a retardation material, since the wavelength of radiation such as ultraviolet rays required for formation differs depending on the structure of the organic compound, the absorption peak of ultraviolet rays derived from the structure of the organic compound is used to maximize the optical anisotropy. Exposure processing has been performed at the wavelength of the maximum region. At this time, when a compound having a maximum absorption peak of ultraviolet light in a short wavelength region (250 to 320 nm) is used, depending on the film thickness, short-wavelength light cannot impart sufficient exposure energy into the film, and the retardation or birefringence amount is insufficient. There was a problem with getting it done.

Japanese Unexamined Patent Publication No. 62-70407 Japanese Unexamined Patent Publication No. 9-208957 Specification of 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

This invention was made|formed in view of the said problem, and aims at providing the manufacturing method of the single-layer retardation material which enables manufacture of a single-layer retardation material with high retardation value and birefringence.

In order to solve the above problems, the inventors of the present invention, as a result of repeated intensive examinations from the viewpoint of the wavelength of polarized ultraviolet rays, used a composition containing a polymer having a photoreactive site that photodimerizes or photoisomerizes with light having a wavelength of 365 nm. In manufacturing a single-layer retardation material, by irradiating polarized ultraviolet rays in which the amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm was controlled to a predetermined amount or less, that is, conventionally for liquid crystal aligning film use By irradiating polarized ultraviolet light having a higher ratio of light with a wavelength of 365 nm than light with a wavelength of 313 nm that is generally used, it was discovered that a single layer retardation material having a high retardation value and refractive index anisotropy (Δn) was obtained, and completed the present invention.

That is, the present invention,

1. (I) a step of applying a polymer composition on a substrate and drying it to form a coating film; and

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

The polymer composition includes a polymer having a photoreactive site in a side chain that undergoes photodimerization or photoisomerization with light having a wavelength of 365 nm,

A method for producing a single layer retardation material, characterized in that the amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm in the polarized ultraviolet light is 10% or less,

2. Manufacturing method of 1 single-layer phase difference material in which the amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm is 5% or less,

3. 1 or 2 methods of producing a single-layer phase difference material in which the polarized ultraviolet rays do not contain light having a wavelength of 313 nm;

4. (III) Method for producing a single layer phase difference material of any one of 1 to 3, including a step of heating the coating film irradiated with the polarized light ultraviolet ray;

5. The method for producing a single layer phase difference material of any one of 1 to 3, wherein the film thickness of the coating film irradiated with the polarized ultraviolet rays is 0.5 µm or more;

6. The manufacturing method of the single layer phase difference material in any one of 1-5 in which the said polymer has a side chain which has any photoreactive site|part represented by following formula (a1) - (a3),

[Formula 1]

(In the formula, A ¹ , A ² and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO-,

L represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms of the alkylene group may each independently be substituted with a halogen atom;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom of this alkylene group may be substituted with a halogen atom;

When T is a single bond, A ² also represents a single bond;

Y ¹ represents a divalent benzene ring;

P ¹ , Q ¹ and Q ² each independently represent a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;

R represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;

In Y ¹ , P ¹ , Q ¹ and Q ² , the hydrogen atom bonded to the benzene ring is each independently a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, or a carbon atom may be substituted with 1 to 5 alkyloxy groups;

X ¹ and X ² each independently represent a single bond, -O-, -COO- or -OCO-;

n1 and n2 are each independently 0, 1 or 2;

When the number of X ¹ is 2, the X ^1s may be the same or different, and when the number of X ² is 2, the X ^2s may be the same or different,

When the number of Q ¹ is 2, the Q ^1s may be the same or different, and when the number of Q ² is 2, the Q ^2s may be the same or different, and the broken line indicates the bond)

7. The manufacturing method of the single layer phase difference material of 6 in which the said polymer has a side chain which does not show photo-alignment property further,

8. The method for producing a single layer phase difference material of 7, which is any one kind of side chain selected from the group consisting of the following formulas (1) to (12), wherein the side chain that does not exhibit the optical orientation is

[Formula 2]

[Formula 3]

(In Formulas (1) to (12), A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O) -, -C(=O)NH-, or -NHC(=O)-, and R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, or a monovalent group. Represents a nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 12 carbon atoms, and R ¹² is a phenyl group, a naphthyl group, a biphenylyl group, or a furanyl group. , a group selected from the group consisting of a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining them, and the hydrogen atom bonded to them is -NO ₂ , -CN, halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms, and 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 biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or a carbon atom of 1 to 12 carbon atoms represents an alkoxy group, E represents -C(=O)O- or -OC(=O)-, d represents an integer of 1 to 12, k1 to k5 are each independently 0 to 2 is an integer, but the sum of k1 to k5 is 2 or more, k6 and k7 are each independently an integer of 0 to 2, but the sum of k6 and k7 is 1 or more, and m1, m2 and m3 are each independently , is an integer of 1 to 3, n is 0 or 1, Z ¹ and Z ² each independently represent a single bond, -C(=O)-, -CH ₂ O- or -CF ₂ - .A broken line indicates a bonding hand.)

9. The method for producing a single layer retardation material of any one of 6 to 8, wherein the side chain having the photoreactive site is a group of any of the following formulas (a1-1) to (a3-1),

[Formula 4]

(In the formula, A ² , L, T, Y ¹ , P ¹ , Q ¹ , R and the broken line represent the same meaning as above)

provides

According to the production method of the present invention, despite the use of polarized ultraviolet light in which the proportion of light with a wavelength of 365 nm is larger than that of light with a wavelength of 313 nm, which has not been generally used in conventional exposure treatment of organic compounds having photoreactive groups, , a single layer retardation material having a high retardation value and birefringence can be obtained.

Hereinafter, the present invention will be specifically described.

The method for producing a single-layer phase difference material of the present invention includes (I) a step of applying a polymer composition on a substrate and drying it to form a coating film, and (II) a step of irradiating the obtained coating film with polarized ultraviolet rays, the polymer composition This includes a polymer having a photoreactive site that photodimerizes or photoisomerizes into light with a wavelength of 365 nm, and occupies the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm in polarized ultraviolet light. It is characterized in that the amount is 10% or less.

[Process (I)]

Step (I) is a step of applying a polymer composition on a substrate to form a coating film. More specifically, the polymer composition is applied to a substrate (eg, a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal (eg, aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, ITO substrate, etc.) or film (eg, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coat, spin coat, flow coat, roll It is applied by a method such as coat, slit coat, spin coat followed by slit coat, inkjet method, or printing method. After application, the coating film can be obtained by air drying or by heating with a heating means such as a hot plate, heat circulation type oven, or IR (infrared ray) type oven to evaporate the solvent. When heating with a heating means, the temperature is not particularly limited, but is preferably 50 to 200°C and more preferably 50 to 150°C.

The polymer composition used in the present invention is a photosensitive side chain type polymer capable of expressing liquid crystallinity, or a mixed side chain type polymer having a liquid crystal side chain polymer and a photosensitive side chain polymer separately (hereinafter simply a side chain type polymer). It is also referred to as a polymer), and the coating film obtained is also a film|membrane which has a side chain type polymer containing liquid crystalline property and photosensitivity. The coating film is not subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. And after polarized light irradiation, it becomes the film (henceforth a single layer phase difference material) to which optical anisotropy was provided through the process of heating the side chain type polymer film. At this time, the minute anisotropy expressed by polarized light irradiation becomes a driving force, and the side chain polymer itself is efficiently reorientated by self-organization. As a result, highly efficient orientation processing is realized as a single-layer retardation material, and a single-layer retardation material to which high optical anisotropy is imparted can be obtained.

As the side chain type polymer, a polymer having a photoreactive site capable of photodimerization or photoisomerization with light having a wavelength of 365 nm is used.

The polymer is not particularly limited as long as it is a side chain type polymer having the above properties, but one having a side chain (hereinafter also referred to as side chain a) having a certain photoreactive site represented by the following formulas (a1) to (a3) is preferable. It is more preferable to have a side chain having any photoreactive site represented by the following formulas (a1-1) to (a3-1).

Also, from the viewpoint of solubility in solvents, the number of benzene rings of the side chain having one photoreactive site is preferably within 3.

[Formula 5]

(In the formula, the broken line represents a bonding hand)

[Formula 6]

(In the formula, the broken line represents a bonding hand)

In each of the above formulas, A ¹ , A ² and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO- indicate

L represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms of this alkylene group may each independently be substituted with a halogen atom.

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom of this alkylene group may be substituted with a halogen atom. In addition, when T is a single bond, A ² is also represents a single bond.

Y ¹ represents a divalent benzene ring.

P ¹ , Q ¹ and Q ² each independently represent a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms.

R represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms.

In Y ¹ , P ¹ , Q ¹ and Q ² , the hydrogen atom bonded to the benzene ring is each independently a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, or a carbon atom It may be substituted with 1 to 5 alkyloxy groups.

X ¹ and X ² each independently represent a single bond, -O-, -COO- or -OCO-.

n1 and n2 are each independently 0, 1 or 2.

When the number of X ¹ is 2, the X ^1s may be the same or different, when the number of X ² is 2, the X ^2s may be the same or different, and when the number of Q ¹ is 2, the Q ^1s are They may be the same or different, and when the number of Q ² is 2, the Q ^2s may be the same or different.

The alkylene group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, etc. can be heard

Specific examples of the alicyclic hydrocarbon ring having 5 to 8 carbon atoms include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring.

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

The alkyl group having 1 to 5 carbon atoms may be either linear or branched, and specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl groups, etc. can be heard

Specific examples of the alkylcarbonyl group having 1 to 5 carbon atoms include methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, and n-pentylcarbonyl groups.

Specific examples of the cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

Specific examples of the alkyloxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and n-pentyloxy groups.

Especially as a polymer, what has a side chain which has a photoreactive site|part represented by any of following formula (a1-1-1) - (a3-1-1) is more preferable.

[Formula 7]

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

The side chain type polymer used in the present invention has a photosensitive side chain bonded to a main chain, and can undergo a crosslinking reaction or an isomerization reaction in response to light having a wavelength of 365 nm. The structure of the photosensitive side chain type polymer is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. When the said side chain type polymer is used as a single layer phase difference material, stable optical anisotropy can be obtained.

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

In addition, the said side chain type polymer may have a side chain (henceforth also called a side chain b) which does not show photo-alignment property.

As such a side chain b, any one type of side chain selected from the group consisting of the following formulas (1) to (12) is preferable, but is not limited thereto.

[Formula 8]

(A broken line indicates a binding hand)

[Formula 9]

(A broken line indicates a binding hand)

In formulas (1) to (12), each of A ³ and A ⁴ independently represents a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)- , -C(=O)NH-, or -NHC(=O)-, and R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, or a monovalent nitrogen represents a containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 12 carbon atoms, and R ¹² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group; It represents a group selected from the group consisting of a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these, and the hydrogen atom bonded to them is -NO ₂ , -CN, or a halogen atom. , may be substituted with an alkyl group of 1 to 5 carbon atoms or an alkoxy group of 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 biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 12 carbon atoms represents a group, E represents -C(=O)O- or -OC(=O)-, d represents an integer of 1 to 12, and k1 to k5 are each independently 0 to 2 Although it is an integer, the sum of k1 to k5 is 2 or more, k6 and k7 are each independently an integer of 0 to 2, but the sum of k6 and k7 is 1 or more, and m1, m2 and m3 are each independently, It is an integer of 1 to 3, n is 0 or 1, Z ¹ and Z ² each independently represent a single bond, -C(=O)-, -CH ₂ O- or -CF ₂ -. Broken lines represent bonded hands.

Specific examples of the monovalent nitrogen-containing heterocyclic group include pyrrolidinyl, piperidinyl, piperazinyl, pyrrolyl, and pyridyl groups. Examples include cyclopentyl and cyclohexyl groups.

Moreover, as an alkyl group and an alkoxy group, the same thing as the group illustrated for said R ^<5> is mentioned.

Among these, as side chain b, what is represented by any of Formulas (1)-(11) is preferable.

The side chain type polymer used in the present invention can be obtained by polymerizing a monomer having a structure represented by any of formulas (a1) to (a3) and, if necessary, a monomer giving side chain b.

Examples of the monomer having a structure represented by any of the formulas (a1) to (a3) (hereinafter also referred to as monomer M1) include compounds represented by the following formulas (M1-1) to (M1-3).

[Formula 10]

(In the formula, A ¹ , A ² , D, L, T, Y ¹ , P ¹ , Q ¹ , Q ² , R, X ¹ , X ² , n1 and n2 represent the same meanings as above)

As monomer M1, any compound represented by the following formulas (M1-1-1) to (M1-3-1) is preferable.

[Formula 11]

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

In particular, any of the compounds represented by the following formulas (M1-1-1-1) to (M1-3-1-1) are more preferable.

[Formula 12]

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

In each of the above formulas, PG is a polymerizable group, and a group selected from groups represented by the following formulas PG1 to PG8 is preferable. Especially, from the point of easy control of a polymerization reaction, and a viewpoint of polymer stability, the acryl group or methacryl group represented by PG1 is preferable.

[Formula 13]

(In the formula, M ¹ represents a hydrogen atom or a methyl group, and the broken line represents a bond with L)

Examples of the monomer (M1-1) include monomers selected from the following formulas A-1-1 to A-1-12. In the following formulas A1-1 to A1-12, PG represents any polymerizable group selected from groups represented by the formulas PG1 to PG8, s1 represents the number of methylene groups, and is an integer of 2 to 9.

[Formula 14]

[Formula 15]

[Formula 16]

Examples of the monomer (M1-2) include monomers selected from the following formulas A-2-1 to A-2-8. In the following formulas A2-1 to A2-8, PG represents a polymerizable group selected from groups represented by the formulas PG1 to PG8, s1 and s2 each independently represent the number of methylene groups, and are an integer of 2 to 9.

[Formula 17]

[Formula 18]

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

Examples of the monomer (M1-3) include monomers selected from the following formulas A-3-1 to A-3-3. In the following formula, PG represents a polymerizable group selected from groups represented by the formulas PG1 to PG8, s1 represents the number of methylene groups, and is an integer of 2 to 9.

[Formula 19]

Specific examples of the monomer (M1-3) include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, and 4-(3-methacryloxyhexyl-1-oxy)cinnamic acid. acryloxypropyl-1-oxy)cinnamic acid, 4-(4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, and the like.

A monomer giving a side chain b that does not exhibit photo-alignment properties (hereinafter also referred to as monomer M2) is a monomer capable of forming a mesogen group at a side chain site.

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

[Formula 20]

More specific examples of the monomer M2 include radical polymerization of hydrocarbons, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. It is preferable that it is a structure which has a structure which consists of a polymeric group derived from at least 1 sort(s) selected from the group which consists of a sexual group and siloxane, and at least 1 sort(s) of Formulas (1)-(12). In particular, it is preferable that monomer M2 has (meth)acrylate as a polymerizable group, and it is preferable that the terminal of a side chain is -COOH.

Preferable examples of the monomer M2 include those represented by the following formulas (M2-1) to (M2-9).

[Formula 21]

(In the formula, PG and s1 represent the same meanings as above.)

[Formula 22]

(In the formula, PG and s1 represent the same meanings as above.)

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

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

Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2, 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , 8-ethyl-8-tricyclodecyl acrylate, etc. are mentioned.

Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthryl methyl methacrylate. , phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methyl Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned.

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

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

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

In the above side chain type polymer, the content of side chain a and side chain b is not particularly limited, but from the viewpoint of photoreactivity, the side chain a is preferably 5 to 99.9 mol%, and more preferably 10 to 95 mol%. desirable. From a viewpoint of photoreactivity, 95 mol% or less of side chain b is preferable.

The side chain type polymer used in the present invention may contain other side chains. The content of the other side chains 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 type polymer is not particularly limited, and a general-purpose method used industrially can be used. Specifically, it can be produced by radical polymerization, cationic polymerization, or anionic polymerization using the monomer M1 described above, if necessary, the monomer M2, and the vinyl group of other monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control and the like.

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

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

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioke. Santhone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, Isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4 ,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxy Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) )-s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-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-dimethylamino Styryl) 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-cyclo Pentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra (t-butylfer Oxycarbonyl) 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) Toxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl- Ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. are mentioned. A radical photoinitiator may be used individually by 1 type, and may mix and use 2 or more types.

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

The organic solvent used for the polymerization reaction is not particularly limited as long as the produced polymer dissolves therein. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-ε-caprolactam. , dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoramide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone , methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono Acetate, 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, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. These organic solvents may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, even if it is a solvent which does not dissolve the produced|generated polymer, you may use it, mixing with the organic solvent mentioned above, to the extent that the produced|generated polymer does not precipitate.

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

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

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

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

The side chain polymer used in the present invention has a weight average molecular weight of 2,000 to 2,000,000 as measured by GPC (Gel Permeation Chromatography) method, considering the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film It is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 200,000.

The polymerizable composition used in the present invention contains the above-mentioned side chain type polymer and an organic solvent (good solvent).

The organic solvent 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, and N-ethyl. -2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N- Dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone , methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol mono Acetate, 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, tetrahydrofuran, tetrahydrofurfuryl alcohol, etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, the said polymer composition may also contain components other than a side chain type polymer and an organic solvent (good solvent). Examples thereof include, but are not limited to, solvents (poor solvents) and compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the phase difference material and the substrate, and the like. don't

Specific examples of solvents (poor solvents) that improve film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl cellosolve. Solve Acetate, Ethyl Cellosolve Acetate, Butyl Carbitol, Ethyl Carbitol, Ethyl Carbitol Acetate, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, di Hexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate , n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxy Propionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypro solvents having low surface tension, such as epoxy)propanol; and the like.

These poor solvents may be used individually by 1 type, or may be used in mixture of 2 or more types.

When using a poor solvent, the content is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass in the solvent so as not to significantly reduce the solubility of the polymer.

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

Specific examples of the compound that improves the adhesion between the phase difference material and the substrate include functional silane-containing compounds, and specific examples thereof include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. , 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3- Aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetriramine, 10-trimethoxysilyl-1,4,7-triaza Decane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate , N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrie Toxysilane etc. are mentioned.

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

Although the specific example of a phenoplast type additive is shown below, it is not limited to these.

[Formula 23]

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

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

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

Examples of photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin and 7-hydroxy 4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones, and aromatic 2-hydroxyketones. -Hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, Thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothia Zoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3 -Methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline , 2-(β-naphthoylmethylene)-3-methylbenzooxazoline, 2-(α-naphthoylmethylene)-3-methylbenzooxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxa Zoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluoro robenzoylmethylene)-3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline, etc.), nitroacenaphthene (5-nitro acenaphthene, etc.), 2-[(m-hydroxy-p-methoxy)styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone, etc. ), naphthalene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merocumarin, and the like. Among these, aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and acetophenoneketals are preferred.

In addition to those described above, in the polymer composition, for the purpose of changing electrical properties such as dielectric constant and conductivity of the phase difference material, as long as the effect of the present invention is not impaired, when used as a dielectric or conductive material, and further, as a phase difference material For the purpose of increasing the hardness and density of the film, a crosslinkable compound may be added.

It is preferable that the said polymer composition is prepared as a coating liquid so that it may become suitable for formation of a single layer phase difference material. That is, the polymer composition used in the present invention is a solvent or compound that improves the side chain type polymer and the above-described film thickness uniformity or surface smoothness, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like, an organic solvent (both It is preferably prepared as a solution dissolved in a solvent).

Here, 1-20 mass % is preferable in a composition, and, as for content of a side chain type polymer, 3-20 mass % is more preferable.

Moreover, the said polymer composition may contain other polymers other than the side chain type polymer mentioned above within the range which does not impair liquid-crystal expression ability and photosensitivity.

As another polymer, the polymer etc. which are not photosensitive side chain type polymers which can express liquid crystal, such as poly(meth)acrylate, a polyamic acid, and a polyimide, are mentioned, for example.

0.5-80 mass % is preferable, and, as for content of the other polymer in all polymer components, 1-50 mass % is more preferable.

[Process (II)]

In step (II), the coating film obtained in step (I) is irradiated with polarized light ultraviolet rays. When irradiating polarized ultraviolet rays to the film surface of a coating film, polarized ultraviolet rays are irradiated through a polarizing plate from a certain direction with respect to a substrate.

In this invention, as the said ultraviolet-ray, as mentioned above, the amount of light with a wavelength of 313 nm which occupies in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm is 10% or less is used.

The amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm in the polarized light to be used is not particularly limited as long as it is 10% or less, but the retardation value and birefringence of the obtained retardation material are further increased. , 5% or less is preferable, 3% or less is more preferable, 1% or less is still more preferable, and it is more preferable that light with a wavelength of 313 nm is not substantially included. In addition, not including substantially means polarized ultraviolet rays obtained by cutting light having a wavelength of 313 nm with a cut filter or the like.

As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

Adjustment of the ratio of wavelengths of polarized ultraviolet rays can be performed by selecting an optimal wavelength ratio through a filter or the like. For example, a band pass filter (BPF) having a central wavelength of 365 nm or a long wave pass filter (LWPF) transmitting wavelengths longer than 313 nm may be used to reduce light having a wavelength of 313 nm.

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

[Process (III)]

In the manufacturing method of this invention, you may be equipped with the process (III) which heats the coating film irradiated with the polarization ultraviolet-ray in process (II). By heating, orientation control ability can be provided to a coating film.

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

The heating temperature can be determined in consideration of the temperature at which the coating film to be used expresses liquid crystallinity, and the temperature at which the side chain type polymer contained in the polymerizable composition to be used expresses liquid crystallinity (hereinafter referred to as liquid crystal expression temperature) It is preferably within the temperature range.

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

In addition, the liquid crystal expression temperature is higher than the liquid crystal transition temperature at which the surface of the polymer or coating film undergoes phase transition from the solid phase to the liquid crystal phase, and is lower than the isotropic phase transition temperature (Tiso) at which the phase transition occurs from the liquid crystal phase to the isotropic phase (isotropic phase). refers to the temperature of For example, expressing liquid crystal at 130 ° C. or lower means that the liquid crystal transition temperature at which a phase transition from a solid phase to a liquid crystal phase occurs is 130 ° C. or lower.

The thickness of the single-layer retardation material produced by the production method of the present invention can be appropriately selected in consideration of the level difference and optical and electrical properties of the substrate used, and for example, 0.5 to 10 μm is suitable, but the polarization used in the present invention Regarding the wavelength characteristics of ultraviolet rays, there is an advantage that even a film thickness of 0.5 μm or more, particularly 3.0 μm or more, reaches the deep portion in the coating film thickness at the time of polarized ultraviolet irradiation in step (II).

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

Example

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

m1, m3, m4, m5, m6 as a monomer having a photoreactive group used in Examples, and m2 as a monomer having a liquid crystalline group are shown below.

m1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. m2 and m3 were synthesized according to the synthesis method described in Unexamined-Japanese-Patent No. 9-118717. m4 is Polymer, 52(25), 5788-5794; It was synthesized by the synthesis method described in 2011. m5 was synthesized by the synthesis method described in Macromolecules 2007, 40, 6355-6360. m6 was synthesized by a synthesis method described in a non-patent literature (Macromolecules 2002, 35, 706-713).

[Formula 24]

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

(organic solvent)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

PGME: Propylene glycol monomethyl ether

PB: propylene glycol monobutyl ether

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

(Surfactants)

R40: Megapack R-40 (manufactured by DIC Co., Ltd.)

(Silane coupling agent)

S-1: 3-glycidoxypropyltriethoxysilane (LS-4668, manufactured by Shin-Etsu Chemical Co., Ltd.)

[1] Synthesis of methacrylate polymer powder

[Synthesis Example 1]

After dissolving m1 (13.3 g, 0.04 mol) and m2 (18.4 g, 0.06 mol) in THF (131.2 g) and degassing with a diaphragm pump, AIBN (0.49 g, 0.003 mol) was added to degas again. conducted. Then, it was made to react at 60 degreeC for 8 hours, and the methacrylate polymer solution was obtained. This polymer solution was added dropwise to methanol (1,000 mL), and the resulting precipitate was filtered. Methacrylate polymer powder P1 was obtained by washing this precipitate with methanol and drying under reduced pressure.

[Synthesis Examples 2 to 5]

Methacrylate polymer powders P2 to P5 were obtained in the same manner as in Synthesis Example 1, except that the monomers and polymerization solvents used were changed as shown in Table 1 below.

[2] Preparation of polymer solution

[Production Example 1-1]

Methacrylate polymer powder P1 (3 g) was added to NMP (7.5 g), and stirred at room temperature for 1 hour to dissolve. Polymer fluid T1 was obtained by adding and stirring PB (1.5g), PGME (1.5g), BC (1.5g), R40 (0.0015g) and S-1 (0.03g) to this solution. This polymer fluid T1 was used as a phase difference material for forming a phase contrast film as it was.

[Production Example 1-2]

Methacrylate polymer powder P2 (3 g) was added to NMP (7.5 g), and stirred at room temperature for 1 hour to dissolve. Polymer fluid T2 was obtained by adding and stirring PB (1.5g), PGME (1.5g), BC (1.5g), R40 (0.0015g) and S-1 (0.03g) to this solution. This polymer fluid T2 was used as a phase difference material for forming a phase contrast film as it was.

[Production Example 1-3]

Methacrylate polymer powder P3 (3 g) was added to NMP (7.5 g) and dissolved by stirring at room temperature for 1 hour. Polymer fluid T3 was obtained by adding and stirring PB (1.5g), PGME (1.5g), BC (1.5g), R40 (0.0015g) and S-1 (0.03g) to this solution. This polymer fluid T3 was used as a retardation material for forming a retardation film as it was.

[Production Example 1-4]

Methacrylate polymer powder P4 (5.0 g) was added to NMP (18.1 g) and dissolved by stirring at room temperature for 1 hour. Polymer fluid T4 was obtained by adding and stirring PB (3.3g), PGME (3.3g), BC (3.3g) and R40 (0.0025g) to this solution. This polymer fluid T4 was used as a phase difference material for forming a phase contrast film as it was.

[Production Example 1-5]

Methacrylate polymer powder P5 (3 g) was added to NMP (7.5 g) and dissolved by stirring at room temperature for 1 hour. Polymer fluid T5 was obtained by adding and stirring PB (1.5g), PGME (1.5g), BC (1.5g), R40 (0.0015g) and S-1 (0.03g) to this solution. This polymer fluid T5 was used as a phase difference material for forming a phase contrast film as it was.

[3] Manufacture of single-layer phase difference material

[Example 1-1]

After filtering the polymer solution T1 with a filter having a pore diameter of 5.0 μm, it was spin-coated on an alkali-free glass substrate and dried on a hot plate at 60° C. for 4 minutes to form a retardation film with a film thickness of 2.0 μm. Subsequently, as shown in Table 3, the coating film surface was irradiated with 365 nm ultraviolet rays through a polarizing plate at 50, 100, 200, 400, 600, 800, and 1000 mJ/cm ² , followed by a heat circulation oven at 140°C. was heated for 20 minutes to prepare a substrate S1 with a retardation film.

[Example 1-2]

Substrate S2 with a retardation film was prepared in the same manner as in Example 1-1, except that a 325 nm long wave pass filter (325LWPF) was used when irradiating with 365 nm ultraviolet rays.

[Example 1-3]

Substrate S3 with a retardation film was prepared in the same manner as in Example 1-2 except that T2 was used for the polymer solution.

[Example 1-4]

Substrate S4 with a retardation film was prepared in the same manner as in Example 1-2 except that T3 was used for the polymer solution.

[Example 1-5]

Substrate S5 with a retardation film was prepared in the same manner as in Example 1-1, except that a 365 nm band pass filter (365BPF) was used when irradiating with 365 nm ultraviolet rays.

[Example 1-6]

After filtering the polymer solution with a filter having a pore size of 5.0 μm using T4, it was spin-coated on a substrate and dried on a hot plate at 60° C. for 4 minutes to form a retardation film with a film thickness of 1.5 μm. Subsequently, as shown in Table 4, the coating film surface was irradiated with ultraviolet rays having a wavelength of 365 nm through a polarizing plate at 50, 100, 200, 400, 800, and 1500 mJ/cm ² , and then in a 130°C heat circulation oven. It was heated for 20 minutes to prepare a substrate S9 with a retardation film.

[Example 1-7]

The polymer solution was filtered through a filter with a pore diameter of 5.0 μm using T5, then spin-coated on a substrate and dried on a hot plate at 60° C. for 4 minutes to form a retardation film with a film thickness of 2.0 μm. Next, as shown in Table 5, ultraviolet rays having a wavelength of 365 nm through a polarizing plate were irradiated to the coating surface at 250, 500, 1000, 2000, 4000, 8000, and 10000 mJ/cm ² using 325LWPF, then 160 It heated for 20 minutes in a heat circulation oven at °C to prepare substrate S11 with a retardation film.

[Comparative Example 1-1]

Substrate S6 with a retardation film was manufactured in the same manner as in Example 1-1, except that the coated film surface was irradiated with ultraviolet light having a wavelength of 313 nm through a polarizing plate.

[Comparative Example 1-2]

Substrate S7 with a retardation film was prepared in the same manner as in Comparative Example 1-1 except that the polymer solution T2 was used.

[Comparative Example 1-3]

Substrate S8 with a retardation film was prepared in the same manner as in Comparative Example 1-1 except that Polymer Fluid T3 was used.

[Comparative Example 1-4]

Substrate S10 with a retardation film was manufactured in the same manner as in Example 1-6, except that the coated film surface was irradiated with ultraviolet rays having a wavelength of 313 nm through a polarizing plate.

[Comparative Example 1-5]

Substrate S12 with a retardation film was prepared in the same manner as in Example 1-7, except that the coating film surface was irradiated with ultraviolet light having a wavelength of 313 nm through a polarizing plate without a cut filter.

A summary of each of the above Examples and Comparative Examples is shown in Table 2.

In addition, the ratio occupied by light with a wavelength of 313 nm in the total amount of irradiation was determined by the following formula.

Ratio (%) occupied by light with a wavelength of 313 nm = radiation intensity with a wavelength of 313 nm / (radiant intensity with a wavelength of 313 nm + radiation intensity with a wavelength of 365 nm) * 100

For each of the substrates S1 to S12 manufactured in each of the above Examples and Comparative Examples, the phase difference value and Δn value were evaluated by the following methods.

(1) Phase difference evaluation

A phase difference value at a wavelength of 550 nm was evaluated using AxoScan manufactured by Axometrics. A result is shown to Tables 3-5.

(2) Δn value evaluation

The degree of orientation (Δn) at a wavelength of 550 nm was calculated by dividing the value of (1) by the film thickness. A result is shown to Tables 6-8.

Claims (9)

(I) a step of applying a polymer composition on a substrate and drying it to form a coating film; and
(II) a step of irradiating the coating film with polarized ultraviolet rays;
The polymer composition includes a polymer having a photoreactive site in a side chain that undergoes photodimerization or photoisomerization with light having a wavelength of 365 nm,
A method for producing a single-layer phase difference material, characterized in that the amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm in the polarization ultraviolet light is 10% or less. According to claim 1,
The manufacturing method of the single-layer phase difference material whose amount of light with a wavelength of 313 nm occupied in the total amount of light with a wavelength of 365 nm and light with a wavelength of 313 nm is 5% or less. According to claim 1 or 2,
The manufacturing method of the single-layer phase difference material in which the said polarization ultraviolet-ray does not contain light with a wavelength of 313 nm. According to any one of claims 1 to 3,
(III) A method for producing a single-layer phase difference material including a step of heating the coating film irradiated with the polarized light ultraviolet ray. According to any one of claims 1 to 3,
The method for producing a single-layer phase difference material in which the film thickness of the coating film irradiated with the polarized ultraviolet rays is 0.5 μm or more. According to any one of claims 1 to 5,
The manufacturing method of the single layer phase difference material in which the said polymer has a side chain which has a certain photoreactive site|part represented by following formula (a1) - (a3).

(In the formula, A ¹ , A ² and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO-,
L represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms of the alkylene group may each independently be substituted with a halogen atom;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom of this alkylene group may be substituted with a halogen atom;
When T is a single bond, A ² also represents a single bond;
Y ¹ represents a divalent benzene ring;
P ¹ , Q ¹ and Q ² each independently represent a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
R represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or an alkyloxy group of 1 to 5 carbon atoms;
In Y ¹ , P ¹ , Q ¹ and Q ² , the hydrogen atom bonded to the benzene ring is each independently a cyano group, a halogen atom, an alkyl group of 1 to 5 carbon atoms, an alkylcarbonyl group of 1 to 5 carbon atoms, or a carbon atom may be substituted with 1 to 5 alkyloxy groups;
X ¹ and X ² each independently represent a single bond, -O-, -COO- or -OCO-;
n1 and n2 are each independently 0, 1 or 2;
When the number of X ¹ is 2, the X ^1s may be the same or different, and when the number of X ² is 2, the X ^2s may be the same or different,
When the number of Q ¹ is 2, the Q ^1s may be the same or different, and when the number of Q ² is 2, the Q ^2s may be the same or different, and the broken line indicates the bond) According to claim 6,
The manufacturing method of the single layer phase difference material in which the said polymer has a side chain which does not show optical orientation. According to claim 7,
The manufacturing method of the single layer phase difference material which is any 1 type of side chain selected from the group which the side chain which does not show the said photo-alignment property consists of following formula (1)-(12).

(In Formulas (1) to (12), A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O) -, -C(=O)NH-, or -NHC(=O)-, and R ¹¹ is -NO ₂ , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, or a monovalent group. Represents a nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 12 carbon atoms, and R ¹² is a phenyl group, a naphthyl group, a biphenylyl group, or a furanyl group. , a group selected from the group consisting of a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining them, and the hydrogen atom bonded to them is -NO ₂ , -CN, halogen atom, an alkyl group of 1 to 5 carbon atoms, or an alkoxy group of 1 to 5 carbon atoms, and 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 biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group of 5 to 8 carbon atoms, an alkyl group of 1 to 12 carbon atoms, or a carbon atom of 1 to 12 carbon atoms represents an alkoxy group, E represents -C(=O)O- or -OC(=O)-, d represents an integer of 1 to 12, k1 to k5 are each independently 0 to 2 is an integer, but the sum of k1 to k5 is 2 or more, k6 and k7 are each independently an integer of 0 to 2, but the sum of k6 and k7 is 1 or more, and m1, m2 and m3 are each independently , is an integer of 1 to 3, n is 0 or 1, Z ¹ and Z ² each independently represent a single bond, -C(=O)-, -CH ₂ O- or -CF ₂ - .A broken line indicates a bonding hand.) According to any one of claims 6 to 8,
The manufacturing method of the single-layer phase difference material in which the side chain which has the said photoreactive site|part is any group represented by following formula (a1-1) - (a3-1).

(In the formula, A ² , L, T, Y ¹ , P ¹ , Q ¹ , R and the broken line represent the same meaning as above)