WO2022080378A1 - Procédé de fabrication d'un matériau à différence de phase monocouche - Google Patents

Procédé de fabrication d'un matériau à différence de phase monocouche Download PDF

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WO2022080378A1
WO2022080378A1 PCT/JP2021/037763 JP2021037763W WO2022080378A1 WO 2022080378 A1 WO2022080378 A1 WO 2022080378A1 JP 2021037763 W JP2021037763 W JP 2021037763W WO 2022080378 A1 WO2022080378 A1 WO 2022080378A1
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group
carbon atoms
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bond
polymer
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大輝 山極
司 藤枝
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日産化学株式会社
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    • 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
    • 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
    • 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 manufacturing a single-layer retardation material, and more specifically, a material having optical characteristics suitable for applications such as a display device and a recording material, particularly a polarizing plate for a liquid crystal display, a retardation plate, and the like.
  • the present invention relates to a method for producing a single-layer retardation material which can be suitably used for an optical compensation film.
  • 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 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 prepare a composition in order to prepare a single-layer retardation material using a composition containing a polymer having a photoreactive moiety that is photodimerized or photoisomerized by ultraviolet rays.
  • a high retardation value and a different refractive index were obtained by irradiating the coating film prepared by using a specific solvent and not completely evaporating the solvent with polarized ultraviolet rays.
  • the present invention has been completed by finding that a single-layer retardation material having a directionality ( ⁇ n) can be obtained.
  • the present invention 1.
  • a polymer having a photoreactive moiety that is photodimerized or photoisomerized by ultraviolet rays in a side chain a solvent having an amide bond, a solvent having a urea bond, a solvent having a sulfoxide bond, a solvent having a cyclic ester structure, and a solvent.
  • a method for producing a single-layer retardation material which comprises an irradiation step, 2.
  • 3. 3. A method for producing a single-layer retardation material having a film thickness of 1 or 2 having a tack property of 0.5 ⁇ m or more. 4.
  • a 1 , A 2 and D independently represent single bonds, -O-, -CH 2- , -COO-, -OCO-, -CONH-, or -NH-CO-, respectively.
  • 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 single bond, 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, a carboxy group, 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 alkyl 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, 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.
  • 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.
  • 6. A method for producing a single-layer retardation material of 5, 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, halogen atom, phenyl group, naphthyl group, biphenylyl group, 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 is represented, and 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.
  • k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more, and k6 and k7 are independently integers of 0 to 2, but k6.
  • k7 are greater than or equal to 1, m1, m2, and m3 are independently integers of 1 to 3, n is 0 or 1, and Z 1 and Z 2 are independent, respectively.
  • Single bond, -C ( O)-, -CH 2 O-, or -CF 2- ; the broken line represents the bond.) 7.
  • a 2 , L, T, Y 1 , P 1 , Q 1 , R and the broken line have the same meanings as described above.
  • a 1 , A 2 and D independently represent single bonds, -O-, -CH 2- , -COO-, -OCO-, -CONH-, or -NH-CO-, respectively.
  • 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 single bond, 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, a carboxy group, 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 alkyl 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, respectively.
  • a polymer composition for a single-layer retardation material wherein the polymer has a side chain that does not further exhibit photoorientity. 10.
  • the polymer composition for a single-layer retardation material in which the side chain showing no photo-orientation 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, halogen atom, phenyl group, naphthyl group, biphenylyl group, 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 is represented, and 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.
  • k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more, and k6 and k7 are independently integers of 0 to 2, but k6.
  • k7 are greater than or equal to 1, m1, m2, and m3 are independently integers of 1 to 3, n is 0 or 1, and Z 1 and Z 2 are independent, respectively.
  • Single bond, -C ( O)-, -CH 2 O-, or -CF 2- ; the broken line represents the bond.) I will provide a.
  • the solvent contained in the polymer composition is from a solvent having an amide bond, a solvent having a urea bond, a solvent having a sulfoxide bond, a solvent having a cyclic ester structure, and a solvent having a cyclic ether structure.
  • a single layer having a high retardation value and double refraction because polarized ultraviolet rays are applied to a coating film having a tack property on the surface, which is prepared by using at least one selected solvent and without completely evaporating the solvent.
  • a retardation material can be obtained.
  • the solute is contained in at least one solvent selected from a solvent having an amide bond, a solvent having a urea bond, a solvent having a sulfoxide bond, a solvent having a cyclic ester structure, and a solvent having a cyclic ether structure. It is presumed that by adopting a peculiar agglomerated state (particularly a state showing rhotropic liquid crystal property) when melted, orientation anisotropy can be induced at the time of coating film, and a film having a high phase difference can be formed.
  • the solvent is presumed that by adopting a peculiar agglomerated state (particularly a state showing rhotropic liquid crystal property) when melted, orientation anisotropy can be induced at the time of coating film, and a film having a high phase difference can be formed.
  • the solvent is presumed that by adopting a peculiar agglomerated state (particularly a state showing rhotropic liquid crystal property) when melted, orientation anisotropy
  • the method for producing a single-layer retardation material of the present invention comprises (I) a polymer having a photoreactive moiety that is photodimerized or photoisomerized by ultraviolet rays in a side chain, a solvent having an amide bond, and a solvent having a urea bond.
  • Step (I) is a step of applying the polymer composition onto the substrate. 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.). It is a step of applying by a method such as a slit coating, a spin coating following the slit coating, an inkjet method, and a printing method.
  • a substrate for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal (for example, aluminum, molybdenum, chromium, etc.)
  • a glass substrate for example
  • 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 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). From the viewpoint of solubility in a solvent, 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 single bond, 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, a carboxy group, 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 alkyl group having 1 to 5 carbon atoms. Represents the alkyloxy group of.
  • 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 cross-linking 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 11 is -NO 2 , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, 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 is represented, and 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.
  • k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more, and k6 and k7 are independently integers of 0 to 2, but k6.
  • k7 are greater than or equal to 1, m1, m2, and m3 are independently integers of 1 to 3, n is 0 or 1, and Z 1 and Z 2 are independent, respectively.
  • Single bond, -C ( O)-, -CH 2 O-, or -CF 2- ; the broken 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 compound represented by the above formula (M1-1) include monomers selected from the following formulas A-1-1 to A-1-13.
  • 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. It is an integer of ⁇ 9.
  • Examples of the compound represented by the above formula (M1-2) include monomers selected from the following formulas A-2-1 to A-2-9.
  • 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. It is an integer from 2 to 9.
  • Examples of the compound represented by the above formula (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, ⁇ -valerolactone, 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.
  • 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 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.
  • 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 comprises a side-chain polymer as described above, a solvent having an amide bond, a solvent having a urea bond, a solvent having a sulfoxide bond, a solvent having a cyclic ester structure, and a cyclic ether structure. It contains at least one solvent selected from the solvents having (hereinafter, these are also collectively referred to as a specific solvent).
  • Specific examples of the solvent having an amide bond include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- ⁇ -caprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2.
  • -Pyrrolidone N-vinyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-2-imidazolidinone and the like can be mentioned.
  • Specific examples of the solvent having a sulfoxide bond include dimethyl sulfoxide and the like.
  • Specific examples of the solvent having a urea bond include tetramethylurea and tetraethylurea.
  • Specific examples of the solvent having a cyclic ester structure include ⁇ -butyrolactone and the like.
  • solvent having a cyclic ether structure examples include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, morpholine, tetrahydrofurfuryl alcohol, tetrahydrofurfurylamine and the like. These may be used alone or in combination of two or more.
  • the polymer composition may contain components other than the side chain polymer and the specific solvent.
  • components other than the side chain polymer and the specific solvent include, but are not limited to, organic solvents other than the above solvents, compounds that improve film thickness uniformity and surface smoothness, and compounds that improve the adhesion between the retardation material and the substrate. ..
  • organic solvents include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, and ethylene glycol.
  • organic solvents may be used alone or in admixture of two or more.
  • the amount used is not particularly limited as long as the desired effect of the present invention is exhibited, but in consideration of obtaining a single-layer retardation material having a high retardation value and birefringence, it is considered. It is preferably 5 to 80% by mass, more preferably 20 to 60% by mass in the total solvent.
  • the solvent used in the polymerizable composition used in the present invention contains a specific solvent as described above, the composition and the content ratio of various solvents are not particularly limited, but the specific solvent may be contained in all the solvents. It is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.
  • 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), Megafuck (registered trademark) F171, F173, F560, F563, R-30, R-40 (DIC).
  • 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.
  • Ketones (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)
  • 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. That is, the polymer composition used in the present invention includes a side chain type polymer, the above-mentioned compound for improving film thickness uniformity and surface smoothness, a compound for improving adhesion between a liquid crystal alignment film and a substrate, and the like. It is preferably prepared as a solution dissolved in a solvent constituting the composition containing a specific solvent.
  • the content of the side chain type polymer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and even more preferably 3 to 10% 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.
  • step (II) drying is performed in such a manner that at least one solvent selected from a solvent having an amide bond, a solvent having a urea bond, a solvent having a sulfoxide bond and a solvent having a cyclic ether structure is not completely vaporized.
  • a coating film having a tack property is formed on the surface.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature is preferably 200 ° C.
  • the heating time is determined in consideration of the heating temperature, it cannot be unconditionally specified, but within the above temperature range, 30 minutes or less is preferable, 15 minutes or less is more preferable, and 10 minutes or less is more preferable. More preferably, 5 minutes or less is further preferable.
  • the coating film produced in the step (II) is not a coating film having no surface tackiness in which the solvent has evaporated as in the conventional method, but a coating film having a sticky surface (tackiness). It is one of the features of the present invention that the coating film is used in the next step.
  • the coating film having a tack property on the surface obtained in the step (II) is irradiated with polarized ultraviolet rays.
  • the substrate is irradiated with polarized ultraviolet rays from a certain direction via a polarizing plate.
  • ultraviolet rays ultraviolet rays having a wavelength in the range of 100 to 400 nm can be used.
  • the optimum wavelength is selected via a filter or the like depending on the type of the coating film to be used.
  • ultraviolet rays having a wavelength in the range of 290 to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the irradiation amount of polarized ultraviolet rays depends on the coating film used. 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 (IV) of heating the coating film irradiated with polarized ultraviolet rays in the step (III). 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 thickness of the coating film when irradiated with polarized ultraviolet rays is preferably 2.5 ⁇ 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 is shown below as the monomer having a photoreactive group used in the examples, and M2 is shown below as the monomer having a liquid crystalline group.
  • M1 was synthesized according to the synthetic method described in International Publication No. 2011/0854546.
  • M2 was synthesized according to the synthesis method described in JP-A-9-118717.
  • the side chain derived from M1 exhibits photoreactivity and liquid crystallinity, and the side chain derived from M2 expresses only liquid crystallinity.
  • Polymer solutions T2 to T11 were obtained in the same manner as in Production Example 1 except that various solvents shown in Table 1 were used instead of NMP. This polymer solution was used as a retardation material for forming a retardation film as it was.
  • Example 2 to 9 Substrates S2 to S8 and S11 with a retardation film were prepared in the same manner as in Example 1 except that the polymer solutions T2 to T8 and T11 were used instead of the polymer solution T1.
  • 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 Table 2.

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Abstract

Un procédé de fabrication d'un matériau à différence de phase monocouche selon la présente invention permet de produire un matériau à différence de phase monocouche ayant une valeur de différence de phase et une biréfringence élevées. Le procédé comprend (I) une étape d'application pour appliquer, sur un substrat, une composition de polymère contenant un polymère ayant, dans une chaîne latérale, un site photoréactif qui est photodimérisisé ou photoisomérisable par des rayons ultraviolets, et au moins un type de solvant choisi parmi un solvant ayant une liaison amide, un solvant ayant une liaison urée, un solvant ayant une liaison sulfoxyde, un solvant ayant une structure d'ester cyclique, et un solvant ayant une structure éther cyclique, (II) une étape de séchage temporaire pour effectuer un séchage sans évaporation complète du solvant, et former un film de revêtement ayant un pouvoir adhésif sur une surface, et (III) une étape d'irradiation pour irradier le film de revêtement ayant un pouvoir adhésif avec des rayons ultraviolets polarisés.
PCT/JP2021/037763 2020-10-13 2021-10-12 Procédé de fabrication d'un matériau à différence de phase monocouche WO2022080378A1 (fr)

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Cited By (1)

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WO2024038887A1 (fr) * 2022-08-18 2024-02-22 日産化学株式会社 Composition polymère et matériau de retardement monocouche

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JP2008276149A (ja) * 2007-04-27 2008-11-13 Hayashi Telempu Co Ltd 高分子フィルム、分子配向素子の作製方法、および液晶配向膜
WO2018043529A1 (fr) * 2016-08-31 2018-03-08 日産化学工業株式会社 Film à différence de phase ayant des propriétés de barrière à la vapeur d'eau, et son procédé de fabrication
WO2020026632A1 (fr) * 2018-08-02 2020-02-06 林テレンプ株式会社 Film à contraste de phase et procédé de production associé
WO2020170874A1 (fr) * 2019-02-22 2020-08-27 林テレンプ株式会社 Corps stratifié optique et son procédé de fabrication
WO2020203628A1 (fr) * 2019-03-29 2020-10-08 日産化学株式会社 Composition polymère et matériau à différence de phase mono-couche
WO2020203631A1 (fr) * 2019-03-29 2020-10-08 日産化学株式会社 Composition polymère et matériau de retard monocouche

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008276149A (ja) * 2007-04-27 2008-11-13 Hayashi Telempu Co Ltd 高分子フィルム、分子配向素子の作製方法、および液晶配向膜
WO2018043529A1 (fr) * 2016-08-31 2018-03-08 日産化学工業株式会社 Film à différence de phase ayant des propriétés de barrière à la vapeur d'eau, et son procédé de fabrication
WO2020026632A1 (fr) * 2018-08-02 2020-02-06 林テレンプ株式会社 Film à contraste de phase et procédé de production associé
WO2020170874A1 (fr) * 2019-02-22 2020-08-27 林テレンプ株式会社 Corps stratifié optique et son procédé de fabrication
WO2020203628A1 (fr) * 2019-03-29 2020-10-08 日産化学株式会社 Composition polymère et matériau à différence de phase mono-couche
WO2020203631A1 (fr) * 2019-03-29 2020-10-08 日産化学株式会社 Composition polymère et matériau de retard monocouche

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024038887A1 (fr) * 2022-08-18 2024-02-22 日産化学株式会社 Composition polymère et matériau de retardement monocouche

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