Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements

Definitions

• the present invention relates to a method for producing a single-layer retardation material, and more specifically, a material having optical properties suitable for applications such as a display device and a recording material, particularly an organic electroluminescence (EL) display device and a liquid crystal display.
• the present invention relates to a method for producing a single-layer retardation material which can be suitably used for an optical compensation film such as a polarizing plate for a display and a retardation plate.
• the polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group. ing.
• Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of irradiating with radiation such as ultraviolet rays to polymerize.
• a method of supporting a specific polymerizable liquid crystal compound having an acrylic group between supports and irradiating with radiation while holding this compound in a liquid crystal state to obtain a polymer (Patent Document 1), or having an acrylic group.
• a method of adding a photopolymerization initiator to a mixture of two types of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with the mixture and irradiating the mixture with ultraviolet rays to obtain a polymer is known (Patent Document 2).
• Patent Documents 3 and 4 an alignment film using a polymerizable liquid crystal compound or a polymer that does not require a liquid crystal alignment film
• Patent Documents 5 and 6 an alignment film using a polymer containing a photocrosslinking site
• Patent Documents 5 and 6 an alignment film using a polymer containing a photocrosslinking site
• the wavelength of ultraviolet rays and other radiation required for formation differs depending on the structure of the organic compound, so in order to maximize optical anisotropy, ultraviolet rays derived from the structure of the organic compound are used.
• the exposure process has been performed at a wavelength in the region where the absorption peak of ultraviolet rays is maximum.
• the short wavelength light may not be able to impart sufficient exposure energy to the inside of the film, resulting in a phase difference or a phase difference. There was a problem that the amount of birefringence was insufficient.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a single-layer retardation material capable of producing a single-layer retardation material having a high retardation value and birefringence.
• the present inventors have a composition containing a polymer having a photoreactive moiety that is photodimerized or photoisomerized with light having a wavelength of 365 nm.
• a composition containing a polymer having a photoreactive moiety that is photodimerized or photoisomerized with light having a wavelength of 365 nm.
• the present invention 1.
• the step of applying the polymer composition on the substrate and drying to form a coating film, and (II) the step of irradiating the coating film with polarized ultraviolet rays are included.
• the polymer composition comprises a polymer having a photoreactive moiety in the side chain that is photodimerized or photoisomerized with light having a wavelength of 365 nm.
• a method for producing a single-layer retardation material wherein the amount of light having a wavelength of 313 nm in the total amount of light having a wavelength of 365 nm and light having a wavelength of 313 nm is 5% or less. 3.
• L represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom of this alkylene group may be independently replaced 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 replaced with a halogen atom.
• a 2 also represents a single bond
• Y 1 represents a divalent benzene ring and represents 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 is a hydrogen atom, a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkyloxy having 1 to 5 carbon atoms.
• the hydrogen atom bonded to the benzene ring is independently a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkylcarbonyl group having 1 to 5 carbon atoms.
• X 1 and X 2 independently represent single bonds, -O-, -COO- or -OCO-, respectively.
• n1 and n2 are 0, 1 or 2, respectively, respectively.
• X 1 may be the same or different, and when the number of X 2 is 2, X 2 may be the same or different.
• Q 1 When the number of Q 1 is 2, Q 1 may be the same or different, and when the number of Q 2 is 2, Q 2 may be the same or different. Represent a hand.
• the method for producing a single-layer retardation material of 7, wherein the side chain that does not exhibit photoalignment is any one of the side chains selected from the group consisting of the following formulas (1) to (12).
• R 11 is -NO 2 , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, 1 A valent nitrogen-containing heterocyclic 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, where R 12 is a phenyl group.
• the hydrogen atom bonded to these may be substituted with -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 13 is a hydrogen atom.
• D represents an integer of 1 to 12
• k1 to k5 are independently integers of 0 to 2
• k6 and k7 are.
• Each independently is an integer of 0 to 2, but the sum of k6 and k7 is 1 or more
• m1, m2 and m3 are independently integers of 1 to 3, and n is 0.
• polarized ultraviolet light having a wavelength of 365 nm which has not been generally used for exposure treatment of organic compounds having a photoreactive group, occupies a larger proportion than light having a wavelength of 313 nm.
• a single-layer retardation material having a high retardation value and birefringence can be obtained.
• the method for producing a single-layer retardation material of the present invention is a step of (I) applying a polymer composition on a substrate and drying to form a coating film, and (II) polarized ultraviolet light on the obtained coating film.
• the polymer composition comprises a polymer having a photoreactive moiety that is photodimerized or photoisomerized with light at a wavelength of 365 nm, comprising light at a wavelength of 365 nm and light at a wavelength of 313 nm in polarized ultraviolet light.
• the amount of light having a wavelength of 313 nm in the total amount of light is 10% or less.
• Step (I) is a step of applying the polymer composition on the substrate to form a coating film. More specifically, the polymer composition is coated on a substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal (for example, aluminum, molybdenum, chromium, etc.)), a glass substrate, a quartz substrate, and the like. Bar coat, spin coat, flow coat, roll coat, etc. on ITO substrate, etc.) or film (for example, resin film such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.).
• TAC triacetyl cellulose
• the coating is applied by a method such as a slit coat, a spin coat following the slit coat, an inkjet method, and a printing method.
• a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven to evaporate the solvent to obtain a coating film.
• the temperature is not particularly limited, but is preferably 50 to 200 ° C, more preferably 50 to 150 ° C.
• the polymer composition used in the present invention is a photosensitive side chain polymer capable of exhibiting liquidity, or a mixed side chain polymer having a liquid crystal side chain polymer and a photosensitive side chain polymer individually.
• a side-chain type polymer a photosensitive side chain polymer capable of exhibiting liquidity
• the obtained coating film is also a film having a side-chain type polymer including liquidity and photosensitivity.
• This coating film is not subjected to a rubbing treatment, but is subjected to an orientation treatment by polarization irradiation.
• the film is subjected to a step of heating the side chain polymer film to obtain a film to which optical anisotropy is imparted (hereinafter, also referred to as a single-layer retardation material).
• a single-layer retardation material a film to which optical anisotropy is imparted
• the slight anisotropy developed by the polarization irradiation becomes the driving force, and the side chain polymer itself is efficiently reoriented by self-assembly.
• highly efficient orientation processing can be realized as a single-layer retardation material, and a single-layer retardation material with high optical anisotropy can be obtained.
• the side chain type polymer a polymer having a photoreactive moiety that is photodimerized or photoisomerized 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 a side chain having any of the photoreactive sites represented by the following formulas (a1) to (a3) (hereinafter referred to as “side chain”). , Also referred to as side chain a), and more preferably having a side chain having any of the photoreactive sites represented by the following formulas (a1-1) to (a3-1).
• the number of benzene rings in the side chain having one photoreactive moiety is preferably 3 or less.
• a 1 , A 2 and D 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 atom of this alkylene group may be independently replaced 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 replaced with a halogen atom.
• 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 is a hydrogen atom, a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkyloxy having 1 to 5 carbon atoms. Represents a group.
• the hydrogen atom bonded to the benzene ring is independently a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkylcarbonyl group having 1 to 5 carbon atoms. , Or may be substituted with an alkyloxy group having 1 to 5 carbon atoms.
• X 1 and X 2 independently represent a single bond, -O-, -COO- or -OCO-, respectively.
• n1 and n2 are 0, 1 or 2, respectively.
• X 1 When the number of X 1 is 2, X 1 may be the same or different, and when the number of X 2 is 2, X 2 may be the same or different, and the number of Q 1 When is 2, Q 1s may be the same or different, and when the number of Q 2s is 2 , 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 and pentane. -1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl group, etc. Be done.
• alicyclic hydrocarbon ring having 5 to 8 carbon atoms examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• the alkyl group having 1 to 5 carbon atoms may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and n-pentyl. Group etc. can be mentioned.
• alkylcarbonyl group having 1 to 5 carbon atoms include methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl group and the like.
• Specific examples of the cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.
• alkyloxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, n-pentyloxy group and the like.
• a polymer having a side chain having a photoreactive site represented by any of the following formulas (a1-1-1) to (a3-1-1) is more preferable.
• the side chain polymer used in the present invention has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction or an isomerization reaction in response to light having a wavelength of 365 nm.
• the structure of the photosensitive side chain polymer is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogen component. Stable optical anisotropy can be obtained when the side chain polymer is used as a single-layer retardation material.
• More specific examples of the structure of the photosensitive side chain polymer include radical polymerizable properties such as (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide and norbornene.
• a structure having a main chain composed of at least one selected from the group consisting of radicals and siloxane and a side chain a is preferable.
• the side chain type polymer may further have a side chain (hereinafter, also referred to as side chain b) that does not exhibit photoalignment.
• a side chain b any one of the side chains selected from the group consisting of the following formulas (1) to (12) is preferable, but the side chain b is not limited thereto.
• R 12 is a phenyl group or naphthyl.
• the hydrogen atom bonded to 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, and R 13 is a hydrogen atom,-.
• d represents an integer of 1 to 12
• k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more
• k6 and k7 are.
• Each independently is an integer of 0 to 2, but the sum of k6 and k7 is 1 or more
• m1, m2 and m3 are independently integers of 1 to 3
• n is 0 or 1
• the dashed line represents the bond.
• the monovalent nitrogen-containing heterocyclic group examples include pyrrolidinyl, piperidinyl, piperazinyl, pyrrolyl, and pyridyl group, and specific examples of the monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms are cyclopentyl. , Cyclohexyl group and the like.
• the alkyl group and the alkoxy group include the same groups as those exemplified in R5 above.
• the side chain b preferably represented by any of the formulas (1) to (11).
• the side chain type polymer used in the present invention can be obtained by polymerizing a monomer having a structure represented by any of the formulas (a1) to (a3) and, if necessary, a monomer giving a side chain b.
• monomer M1 As the monomer having the structure represented by any of the formulas (a1) to (a3) (hereinafter, also referred to as monomer M1), the compounds represented by the following formulas (M1-1) to (M1-3) are used. Can be mentioned.
• any compound represented by the following formulas (M1-1-1) to (M1-3-1) is preferable.
• any compound represented by the following formulas (M1-1-1-1) to (M1-3-1-1) is more preferable.
• PG is a polymerizable group, and a group selected from the groups represented by the following formulas PG1 to PG8 is preferable. Among them, an acrylic group or a methacrylic group represented by PG1 is preferable from the viewpoint of easy control of the polymerization reaction and the stability of the polymer.
• 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.
• PG represents any polymerizable group selected from the groups represented by the above formulas PG1 to PG8, and s1 represents the number of methylene groups and is an integer of 2 to 9. Is.
• Examples of the monomer (M1-2) include monomers selected from the following formulas A-2-1 to A-2-8.
• PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, and s1 and s2 each independently represent the number of methylene groups of 2 to 9. It is an integer.
• Examples of the monomer (M1-3) include monomers selected from the following formulas A-3-1 to A-3-3.
• PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, and s1 represents the number of methylene groups, which is an integer of 2 to 9.
• Specific examples of the above-mentioned monomer (M1-3) include 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acrylicoxyhexyl-1-oxy) cinnamic acid, and 4- (6-(6-methacrylicoxyhexyl-1-oxy) cinnamic acid. Examples thereof include 3-methacryloxypropyl-1-oxy) cinnamic acid and 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.
• the monomer that gives the side chain b that does not show photo-orientation (hereinafter, also referred to as monomer M2) is a monomer that can form a mesogen group at the side chain site.
• the mesogen group having a side chain even if it is a group having a mesogen structure by itself such as biphenyl or phenylbenzoate, it is a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid. May be good.
• the following structure is preferable as the mesogen group contained in the side chain.
• the monomer M2 include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and other radically polymerizable groups and siloxanes. It is preferable that the structure has a structure consisting of a polymerizable group derived from at least one selected from the group and at least one of the formulas (1) to (12).
• the monomer M2 preferably has a (meth) acrylate as a polymerizable group, and preferably has a -COOH end in the side chain.
• Preferred examples of the monomer M2 include those represented by the following formulas (M2-1) to (M2-9).
• other monomers can be copolymerized as long as the photoreactiveness and / or liquid crystallinity development ability is not impaired.
• examples of other monomers include industrially available radical polymerization-reactive monomers.
• Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds, vinyl compounds and the like.
• unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
• acrylic acid ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-.
• vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
• styrene compound examples include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene and the like.
• maleimide compound examples include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.
• the contents of the side chain a and the side chain b are not particularly limited, but the side chain a is preferably 5 to 99.9 mol% from the viewpoint of photoreactivity. 10-95 mol% is more preferred. From the viewpoint of photoreactivity, the side chain b is preferably 95 mol% or less.
• the side chain type polymer used in the present invention may contain other side chains.
• the content of the other side chains is the rest when the total content of the side chains a and b is less than 100 mol%.
• the method for producing the side chain polymer is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by radical polymerization, cationic polymerization or anionic polymerization using the vinyl group of the above-mentioned monomer M1, the monomer M2 and other monomers as needed. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.
• a known compound such as a radical polymerization initiator (radical thermal polymerization initiator, radical photopolymerization initiator) or a reversible addition-cleaving chain transfer (RAFT) polymerization reagent shall be used. Can be done.
• a radical polymerization initiator radiation thermal polymerization initiator, radical photopolymerization initiator
• RAFT reversible addition-cleaving chain transfer
• the radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature.
• examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation).
• the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
• examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone and 2-hydroxy.
• 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 and the like can be used.
• the organic solvent used in the polymerization reaction is not particularly limited as long as the produced polymer can be dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, dimethylsulfoxide, and tetramethylurea.
• Ppyridine dimethyl sulfone, hexamethylphosphoramide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, Methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol.
• 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, ethylisobutyl ether, diisobutylene , Amilacetate, butylbutyrate, butyl ether, diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane
• the solvent may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
• oxygen in the organic solvent causes the polymerization reaction to be inhibited, so it is preferable to use an organic solvent that has been degassed to the extent possible.
• the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 to 150 ° C, but is preferably in the range of 50 to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial reaction can be carried out at a high concentration and then an organic solvent can be added.
• the ratio of the radical polymerization initiator when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 to 20 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.
• the polymer produced from the reaction solution obtained by the above reaction can be recovered by pouring the reaction solution into a poor solvent and precipitating it, but this reprecipitation treatment is not essential.
• the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like.
• the polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
• impurities in the polymer can be reduced.
• the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the efficiency of purification is further improved.
• the side chain polymer used in the present invention has a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film. It is preferably 2,000 to 2,000,000, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 200,000.
• GPC Gel Permeation Chromatography
• the polymerizable composition used in the present invention contains the side chain type polymer as described above 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- ⁇ -caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-.
• Vinyl-2-pyrrolidone dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-Butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethylamylketone, methylnonylketone, methylethylketone, methylisoamylketone, methylisopropylketone, cyclohexanone, cyclopentanone, ethylene carbonate , Propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glyco
• the polymer composition may contain components other than the side chain type polymer and the organic solvent (good solvent).
• examples thereof include a solvent (poor solvent) that improves the film thickness uniformity and surface smoothness when the polymer composition is applied, a compound, and a compound that improves the adhesion between the retardation material and the substrate.
• a solvent poor solvent
• the adhesion between the retardation material and the substrate it is not limited to these.
• These poor solvents may be used alone or in combination of two or more.
• the content thereof is preferably 5 to 80% by mass, more preferably 20 to 60% by mass in the solvent so as not to significantly reduce the solubility of the polymer.
• Examples of the compound that improves the film thickness uniformity and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. Specific examples of these include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafuck (registered trademark) F171, F173, F560, F563, R-30, R-40 (registered trademark).
• the content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the side chain polymer.
• the compound that improves the adhesion between the retardation material and the substrate include functional silane-containing compounds, and specific examples thereof include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
• a phenoplast-based compound or an epoxy group-containing compound is added to the polymer composition for the purpose of preventing deterioration of the characteristics due to the backlight when the polarizing plate is formed. It may be added.
• epoxy group-containing compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, Dibromoneopentyl Glycol Diglycidyl Ether, 1,3,5,6-Tetraglycidyl-2,4-Hexanediol, N, N, N', N'-Tetra
• examples thereof include glycidyl-m-xylylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl
• the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the side chain type polymer contained in the polymer composition, and 1 to 20 parts by mass. Parts by mass are more preferred. If the content is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal display may deteriorate.
• a photosensitizer can also be used as an additive.
• a colorless sensitizer and a triplet sensitizer are preferable.
• photosensitizer examples include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscmarin, aromatic 2-hydroxyketone, and aromatic 2-hydroxy.
• Ketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthron, thiazolin (2-benzoylmethylene-3-methyl- ⁇ - Naftthiazolin, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazolin, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazolin, 2- (4-biphenoylmethylene) -3-methylbenzothiazolin , 2- ( ⁇ -naphthoyl methylene) -3
• aromatic 2-hydroxyketone (benzophenone), coumarin, ketokumarin, carbonylbisquemarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal are preferred.
• the polymer composition includes a dielectric or a conductive substance for the purpose of changing the electrical properties such as the dielectric constant and the conductivity of the retardation material as long as the effect of the present invention is not impaired.
• a crosslinkable compound may be added for the purpose of increasing the hardness and the density of the film when it is used as a retardation material.
• the polymer composition is preferably prepared as a coating liquid so as to be suitable for forming a single-layer retardation material.
• the polymer composition used in the present invention includes a side chain type polymer, a solvent or compound that improves the film thickness uniformity and surface smoothness described above, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.
• the solution is prepared as a solution dissolved in an organic solvent (good solvent).
• the content of the side chain type polymer is preferably 1 to 20% by mass, more preferably 3 to 20% by mass in the composition.
• the polymer composition may contain other polymers as long as the liquid crystal display ability and photosensitive performance are not impaired.
• other polymers include polymers such as poly (meth) acrylate, polyamic acid, and polyimide, which are not photosensitive side chain polymers capable of exhibiting liquid crystallinity.
• the content of the other polymer in the total polymer component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass.
• the coating film obtained in the step (I) is irradiated with polarized ultraviolet rays.
• the substrate is irradiated with polarized ultraviolet rays from a certain direction via a polarizing plate.
• the ultraviolet rays as described above, the amount of light having a wavelength of 313 nm in the total amount of light having a wavelength of 365 nm and light having a wavelength of 313 nm is 10% or less.
• the amount of light having a wavelength of 313 nm in the total amount of light having a wavelength of 365 nm and light having a wavelength of 313 nm in the polarized ultraviolet rays used is not particularly limited as long as it is 10% or less, but the phase difference value of the obtained retardation material is not particularly limited. And from the viewpoint of further enhancing birefringence, 5% or less is preferable, 3% or less is more preferable, 1% or less is even more preferable, and it is further preferable that light having a wavelength of 313 nm is substantially not contained.
• substantially free means polarized ultraviolet rays obtained by cutting light having a wavelength of 313 nm with a cut filter or the like.
• the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
• the wavelength ratio of the polarized ultraviolet rays can be adjusted by selecting the optimum wavelength ratio via a filter or the like.
• light having a wavelength of 313 nm may be reduced by using a bandpass filter (BPF) having a center wavelength of 365 nm, a long wavepass filter (LWPF) that transmits a wavelength longer than 313 nm, or the like.
• BPF bandpass filter
• LWPF long wavepass filter
• 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 realizes the maximum value of ⁇ A, which is the difference between the ultraviolet absorptance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorptivity in the vertical direction in the coating film. It is preferably in the range of%, and more preferably in the range of 1 to 50%.
• the production method of the present invention may include a step (III) of heating the coating film irradiated with polarized ultraviolet rays in the step (II). Orientation control ability can be imparted to the coating film by heating.
• a heating means a hot plate, a heat circulation type oven, an IR (infrared) type oven or the like can be used.
• the heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is developed, and the temperature at which the side chain type polymer contained in the polymerizable composition to be used develops liquid crystal color (hereinafter, liquid crystal expression). It is preferably within the temperature range of). In the case of a thin film surface such as a coating film, the liquid crystal development temperature on the coating film surface is expected to be lower than the liquid crystal development temperature when the side chain polymer is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature on the surface of the coating film.
• the temperature range of the heating temperature after irradiation with polarized ultraviolet rays has a lower limit of 10 ° C lower than the lower limit of the temperature range of the liquid crystal development temperature of the side chain polymer, and an upper limit of a temperature 10 ° C lower than the upper limit of the liquid crystal temperature range.
• the temperature in the range is preferable. If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high above the above temperature range, the state of the coating film is in a state. Tends to be close to an isotropic liquid state (isotropic phase), in which case self-assembly can make it difficult to reorient in one direction.
• the liquid crystal development temperature is equal to or higher than the liquid crystal transition temperature at which the surface of the polymer or the coating film undergoes a phase transition from the solid phase to the liquid crystal phase, and the isotropic phase undergoes a phase transition from the liquid crystal phase to the isotropic phase.
• the temperature below the phase transition temperature (Tiso).
• exhibiting liquid crystallinity at 130 ° C. or lower means that the liquid crystal transition temperature at which a phase transition occurs from the solid phase to the liquid crystal phase is 130 ° C. or lower.
• the thickness of the single-layer retardation material produced by the production method of the present invention can be appropriately selected in consideration of the step of the substrate to be used and the optical and electrical properties, and is preferably 0.5 to 10 ⁇ m, for example.
• the coating film thickness at the time of irradiation with the polarized ultraviolet rays in the step (II) reaches a deep part even if the film thickness is 0.5 ⁇ m or more, particularly 3.0 ⁇ m or more.
• the single-layer retardation material obtained by the above-described manufacturing method is a material having optical characteristics suitable for applications such as display devices and recording materials, and in particular, optical compensation for polarizing plates and retardation plates for liquid crystal displays. Suitable as a film.
• M1, m3, m4, m5, and m6 are shown below as the monomers having photoreactive groups used in the examples, and m2 is shown below as the monomers having liquidity groups.
• m1 was synthesized according to the synthetic method described in International Publication No. 2011/0854546.
• m2 and m3 were synthesized according to the synthesis method described in JP-A-9-118717.
• m4 was synthesized by the synthetic method described in Polymer, 52 (25), 5788-5794; 2011.
• m5 was synthesized by the synthetic method described in Macromolecules 2007, 40, 6355-6360.
• m6 was synthesized by the synthetic method described in the non-patent document (Macromolecules 2002, 35, 706-713).
• Methacrylate polymer powder P5 (3 g) was added to NMP (7.5 g), and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, PB (1.5 g), PGME (1.5 g), BC (1.5 g), R40 (0.0015 g) and S-1 (0.03 g) are added, and the mixture is stirred to obtain a polymer solution. I got T5. This polymer solution T5 was used as a retardation material for forming a retardation film as it was.
• Example 1-1 Manufacture of single-layer retardation material
• the polymer solution T1 was filtered through a filter having a pore size of 5.0 ⁇ m, spin-coated on a non-alkali glass substrate, and dried on a hot plate at 60 ° C. for 4 minutes to form a retardation film having a film thickness of 2.0 ⁇ m.
• the coating film surface was irradiated with ultraviolet rays of 365 nm through the polarizing plate at 50, 100, 200, 400, 600, 800, 1000 mJ / cm 2 , and then heat circulation at 140 ° C.
• the substrate S1 with a retardation film was prepared by heating in a formula oven for 20 minutes.
• Example 1-2 A substrate S2 with a retardation film was produced in the same manner as in Example 1-1 except that a 325 nm long wave pass filter (325 LWPF) was used when irradiating with ultraviolet rays of 365 nm.
• 325 LWPF 325 nm long wave pass filter
• Example 1-3 A substrate S3 with a retardation film was prepared in the same manner as in Example 1-2 except that T2 was used as the polymer solution.
• Example 1-4 A substrate S4 with a retardation film was prepared in the same manner as in Example 1-2 except that T3 was used as the polymer solution.
• Example 1-5 A substrate S5 with a retardation film was produced in the same manner as in Example 1-1 except that a 365 nm bandpass filter (365BPF) was used when irradiating with ultraviolet rays of 365 nm.
• 365BPF 365 nm bandpass filter
• Example 1-6 The polymer solution was filtered using T4 with a filter having a pore size of 5.0 ⁇ m, spin-coated on the substrate, and dried on a hot plate at 60 ° C. for 4 minutes to form a retardation film having a film thickness of 1.5 ⁇ m.
• ultraviolet rays having a wavelength of 365 nm are irradiated to the coating film surface through a polarizing plate at 50, 100, 200, 400, 800, 1500 mJ / cm 2 , and then a heat circulation method at 130 ° C. is performed.
• the substrate S9 with a retardation film was prepared by heating in an oven for 20 minutes.
• Example 1-7 The polymer solution was filtered using T5 with a filter having a pore size of 5.0 ⁇ m, spin-coated on the substrate, and dried on a hot plate at 60 ° C. for 4 minutes to form a retardation film having a film thickness of 2.0 ⁇ m. Then, after irradiating the coating film surface with ultraviolet rays having a wavelength of 365 nm via a polarizing plate at 250,500,1000,2000,4000,8000,10000 mJ / cm 2 as shown in Table 5, using 325 LWPF. , The substrate S11 with a retardation film was prepared by heating in a heat circulation type oven at 160 ° C. for 20 minutes.
• Example 1-1 A substrate S6 with a retardation film was produced in the same manner as in Example 1-1 except that the coating film surface was irradiated with ultraviolet rays having a wavelength of 313 nm via a polarizing plate.
• Comparative Example 1-2 A substrate S7 with a retardation film was produced in the same manner as in Comparative Example 1-1 except that the polymer solution T2 was used.
• Comparative Example 1-3 A substrate S8 with a retardation film was produced in the same manner as in Comparative Example 1-1 except that the polymer solution T3 was used.
• Example 1-4 A substrate S10 with a retardation film was produced in the same manner as in Example 1-6 except that the coating film surface was irradiated with ultraviolet rays having a wavelength of 313 nm via a polarizing plate.
• Example 1-5 A substrate S12 with a retardation film was produced in the same manner as in Example 1-7 except that the coating film surface was irradiated with ultraviolet rays having a wavelength of 313 nm via a polarizing plate without a cut filter.
• Table 2 shows a summary of each of the above examples and comparative examples.
• phase difference value and ⁇ n value of the substrates S1 to S12 produced in each of the above Examples and Comparative Examples were evaluated by the following methods.
• phase difference evaluation The phase difference value at a wavelength of 550 nm was evaluated using AxoScan manufactured by Axometrics. The results are shown in Tables 3-5.

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