WO2020203628A1 - Composition polymère et matériau à différence de phase mono-couche - Google Patents

Composition polymère et matériau à différence de phase mono-couche Download PDF

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Publication number
WO2020203628A1
WO2020203628A1 PCT/JP2020/013612 JP2020013612W WO2020203628A1 WO 2020203628 A1 WO2020203628 A1 WO 2020203628A1 JP 2020013612 W JP2020013612 W JP 2020013612W WO 2020203628 A1 WO2020203628 A1 WO 2020203628A1
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group
carbon atoms
side chain
polymer
polymer composition
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PCT/JP2020/013612
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English (en)
Japanese (ja)
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隆之 根木
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日産化学株式会社
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Priority to KR1020217031725A priority Critical patent/KR20210148158A/ko
Priority to CN202080020046.3A priority patent/CN113557265B/zh
Priority to JP2021511907A priority patent/JPWO2020203628A1/ja
Publication of WO2020203628A1 publication Critical patent/WO2020203628A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

  • the present invention relates to a composition containing a polymer and a single-layer retardation material.
  • a material having optical properties suitable for applications such as display devices and recording materials particularly a liquid crystal polymer that can be suitably used for an optical compensation film such as a polarizing plate for a liquid crystal display and a retardation plate, the polymer.
  • the present invention relates to a composition containing the above, and a single-layer retardation material obtained from the composition.
  • 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 state to obtain a polymer Patent Document 1
  • a method is known in which a photopolymerization initiator is added 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 the polymer is obtained by irradiating with ultraviolet rays (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 photocrosslinked site
  • Various single-layer coating type alignment films have been reported.
  • the film preparation process is difficult, it is necessary to use a solvent having excellent dissolving power such as NMP, chloroform, chlorobenzene, etc. as the solvent of the polymer used, and there are problems such as low solubility of the polymer. Yes, no material has been found to solve such problems.
  • the present invention has been made in view of the above problems, and a novel polymer capable of producing a single-layer retardation material having a high retardation value by a simpler process, a composition containing the polymer, and the composition. It is an object of the present invention to provide a single layer retardation material obtained from an object.
  • the present inventor uses a composition containing a specific polymer and a specific additive to obtain a high refractive index anisotropy without using a liquid crystal alignment film.
  • the present invention has been completed by finding that a single-layer retardation material having a property ( ⁇ n) can be obtained and that a single-layer retardation material having a high retardation value and no turbidity can be produced under low temperature conditions. ..
  • the present invention provides the following polymer compositions and single-layer retardation materials.
  • R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group, and in R 1 .
  • R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
  • R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and c ⁇ . When it is 2, each R may be the same as or different from each other.
  • a is 0, 1 or 2.
  • b is 0 or 1.
  • c is an integer satisfying 0 ⁇ c ⁇ 2b + 4.
  • the dashed line is the join hand.
  • the polymer composition of 1 in which the side chain having the photoreactive site is represented by the following formula (a1). (In the formula, R 1 , R 2 and a are the same as above.
  • the benzene ring in the formula (a1) includes an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and the like. It may be substituted with a substituent selected from nitro groups.
  • the dashed line is the join hand.
  • (A) A polymer composition of 1 or 2 in which the side chain type polymer further has a side chain that expresses only liquid crystallinity. 4.
  • the polymer composition of 3 in which the side chain expressing only the liquid crystal property is the liquid crystal side chain represented by any of the following formulas (1) to (13).
  • R 11 is -NO 2 , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon.
  • R 12 is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these.
  • a group selected from the above, and the hydrogen atom bonded to these may be substituted with -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more.
  • k6 and k7 are independently integers of 0 to 2, but the total of k6 and k7 is 1 or more.
  • m1, m2 and m3 are independently integers of 1 to 3.
  • n is 0 or 1.
  • the dashed line is the join hand.
  • the polymer composition of 4 in which the side chain expressing only the liquid crystal property is the liquid crystal side chain represented by any of the formulas (1) to (11). 6.
  • a step of applying the polymer composition of any one of 1 to 5 on a substrate to form a coating film (I) A step of applying the polymer composition of any one of 1 to 5 on a substrate to form a coating film.
  • a method for producing a single-layer retardation material which comprises (II) a step of irradiating the coating film with polarized ultraviolet rays, and (III) a step of heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.
  • a single-layer retardation material obtained from any of the compositions of 7.1-5.
  • the present invention it is possible to provide a single-layer retardation material having a high retardation value even if it is a thin film, and a polymer that gives it.
  • the polymer composition of the present invention has a photosensitive side chain polymer capable of exhibiting liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the above polymer composition is used.
  • the obtained coating film is a film having a photosensitive side chain polymer capable of exhibiting liquid crystallinity.
  • This coating film is subjected to an orientation treatment by polarization irradiation without performing a rubbing treatment. Then, after the polarization irradiation, the side chain polymer film is heated to obtain a film having optical anisotropy (hereinafter, also referred to as a single-layer retardation material).
  • the polymer composition of the present invention contains a silane coupling agent as the component (B) together with the side chain type polymer of the component (A).
  • the silane coupling agent floats during film formation. That is, they are unevenly distributed on the surface that does not come into contact with the substrate.
  • the aggregation of the polymer on the surface is suppressed, so that the flatness of the obtained retardation material is improved.
  • haze is suppressed. It should be noted that these include the inventor's views on the mechanism of the present invention and are not binding on the present invention.
  • the polymer composition of the present invention is characterized by containing (A) a side chain polymer having a side chain having a photoreactive site, (B) a silane coupling agent, and (C) an organic solvent.
  • the component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a side chain having a photoreactive moiety represented by the following formula (a) (hereinafter, side chain). It is a side chain polymer having (also referred to as a).
  • R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group.
  • -CH 2- may be the terminal -CH 2- in R 1 .
  • R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
  • R is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and c ⁇ .
  • each R may be the same as or different from each other.
  • a is 0, 1 or 2.
  • b is 0 or 1.
  • c is an integer satisfying 0 ⁇ c ⁇ 2b + 4.
  • the dashed line is the join hand.
  • the alkylene group having 1 to 30 carbon atoms represented by R 1 may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and the like.
  • Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9 -Diyl group, decane-1,10-diyl group and the like can be mentioned.
  • Examples of the divalent aromatic group represented by R 2 include a phenylene group and a biphenylylene group.
  • Examples of the divalent alicyclic group represented by R 2 include a cyclohexanediyl group and the like.
  • Examples of the divalent heterocyclic group represented by R 2 include a frangyl group.
  • Examples of the divalent fused cyclic group represented by R 2 include a naphthylene group and the like.
  • side chain a one represented by the following formula (a1) (hereinafter, also referred to as side chain a1) is preferable.
  • R 1, R 2 and a are as defined above.
  • the benzene ring in the formula (a1) includes an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and the like. It may be substituted with a substituent selected from nitro groups.
  • the dashed line is the join hand.
  • side chain a1 for example, one represented by the following formula (a1-1) is preferable.
  • L is a linear or branched alkylene group having 1 to 16 carbon atoms.
  • the side chain polymer (A) preferably reacts with light in the wavelength range of 250 to 400 nm and exhibits liquid crystallinity in the temperature range of 100 to 300 ° C.
  • the side chain polymer (A) preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 to 400 nm.
  • the side chain type polymer has a side chain having photosensitivity bonded to the main chain, and can cause a cross-linking reaction or an isomerization reaction in response to light.
  • the structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogen component. When the side chain polymer is used as a single-layer retardation material, stable optical anisotropy can be obtained.
  • the structure of the photosensitive side chain polymer capable of exhibiting liquidity include (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, and the like. It is preferable that the structure has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and siloxane, and a side chain a.
  • the side chain type polymer (A) exhibits liquid crystallinity in a temperature range of 100 to 300 ° C.
  • a side chain hereinafter, also referred to as side chain b
  • “expressing only liquid crystallinity” means that the polymer having only the side chain b is used in the process for producing the retardation material of the present invention (that is, steps (I) to (III) described later). It means that it does not show photosensitivity and only develops liquid crystallinity.
  • any one liquid crystal side chain selected from the group consisting of the following formulas (1) to (13) is preferable.
  • R 11 is -NO 2 , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon.
  • R 12 is a group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these.
  • a group selected from the above, and the hydrogen atom bonded to these may be substituted with -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • k1 to k5 are independently integers of 0 to 2, but the total of k1 to k5 is 2 or more.
  • k6 and k7 are independently integers of 0 to 2, but the total of k6 and k7 is 1 or more.
  • m1, m2 and m3 are independently integers of 1 to 3.
  • n is 0 or 1.
  • the side chain b is preferably one represented by any of the formulas (1) to (11).
  • the side chain polymer of the component (A) can be obtained by polymerizing a monomer having a structure represented by the formula (a) and, if desired, a monomer having a structure expressing only liquid crystallinity.
  • Examples of the monomer having a structure represented by the formula (a) include a compound represented by the following formula (M1). (In the formula, R 1 , R 2 , R 3 , R, a, m and n are the same as above.)
  • PL is a polymerizable group represented by any of the following formulas (PL-1) to (PL-5).
  • Q 1, Q 2 and Q 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or straight-substituted with halogen It is a chain or branched alkyl group having 1 to 10 carbon atoms.
  • the broken line is the bond with R 1 or L.
  • Preferred examples of the monomer M1 include those represented by the following formulas (M1-1) to (M1-5). (In the formula, PL is the same as above. P is an integer from 2 to 9.)
  • a monomer having a structure that expresses only liquid crystal properties (hereinafter, also referred to as monomer M2) is a monomer in which a polymer derived from the monomer expresses liquid crystal properties and the polymer can form a mesogen group at a side chain site. That is.
  • 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 consist of radically polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and siloxane. It is preferable that the structure has a structure consisting of a polymerizable group derived from at least one selected from the group and at least one of the formulas (1) to (13).
  • the monomer M2 preferably has a (meth) acrylate as a polymerizable group, and preferably has a side chain terminal of ⁇ COOH.
  • Preferred examples of the monomer M2 include those represented by the following formulas (M2-1) to (M2-11).
  • other monomers can be copolymerized as long as the photoreactiveness and / or liquid crystallinity expression ability is not impaired.
  • examples of other monomers include industrially available radical polymerization-reactive monomers.
  • Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds, vinyl compounds and the like.
  • 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-butyl.
  • methacrylate 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-butyl.
  • Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
  • Examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene and the like.
  • Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.
  • the content of the side chain a in the side chain polymer of the present invention is preferably 20 to 99.9 mol%, more preferably 30 to 95 mol%, and further 40 to 90 mol% from the viewpoint of photoreactivity. preferable.
  • the content of the side chain b in the side chain polymer of the present invention is preferably 0.1 to 80 mol%, more preferably 5 to 70 mol%, and further preferably 10 to 60 mol% from the viewpoint of the retardation value. preferable.
  • the side chain polymer of the present invention may contain other side chains.
  • the content of the other side chains is the rest of the contents of the side chains a and b when the total content is less than 100 mol%.
  • the method for producing the side chain polymer of the component (A) is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by radical polymerization, cationic polymerization or anionic polymerization using the vinyl groups of the above-mentioned monomers M1 and M2 and, if desired, other monomers. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.
  • a known compound such as a radical polymerization initiator (radical thermal polymerization initiator, radical photopolymerization initiator) or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent shall be used. Can be done.
  • a radical polymerization initiator radiation thermal polymerization initiator, radical photopolymerization initiator
  • RAFT reversible addition-cleavage chain transfer
  • the radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature.
  • 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 massive polymerization method, a solution polymerization method and the like can be used.
  • the organic solvent used in the polymerization reaction is not particularly limited as long as the produced polymer dissolves. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, dimethylsulfoxide, and tetramethylurea.
  • the above organic solvent may be used alone or in combination of two or more. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. Further, in radical polymerization, oxygen in an organic solvent causes an inhibition of the polymerization reaction, so it is preferable to use an organic solvent degassed to the extent possible.
  • the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 to 150 ° C, but is preferably in the range of 50 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high mass, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration and then an organic solvent can be added.
  • 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 of the radical polymerization initiator is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.
  • the reaction solution may be put into a poor solvent to precipitate the polymers.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like.
  • the polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the purification efficiency is further improved.
  • the side chain polymer (A) of the present invention has a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of coating film formation, and uniformity of the coating film.
  • GPC Gel Permeation Chromatography
  • 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.
  • the polymer composition of the present invention contains (B) a silane coupling agent.
  • a silane coupling agent a silane compound represented by the following formula (B) is preferable.
  • R 21 is a reactive functional group.
  • R 22 is a hydrolyzable group.
  • R 23 is a methyl group or an ethyl group.
  • x is an integer of 0 to 3.
  • y is an integer of 1 to 3.
  • Examples of the reactive functional group represented by R 21 include an amino group, a ureido group, a (meth) acryloxy group, a vinyl group, an epoxy group, a mercapto group and a group having an oxetane structure, and examples thereof include an amino group, a ureido group and (Meta) Acryloyloxy groups, groups having an oxetane structure and the like are preferable. A group having an oxetane structure is particularly preferable.
  • Examples of the hydrolyzable group represented by R 22 include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms.
  • Examples of the halogen atom include a chlorine atom and a bromine atom.
  • the alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically, it is a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.
  • Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms are a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group and a 2-ethoxyethoxy group.
  • silane coupling agent examples include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldi.
  • silane coupling agent a commercially available product can be used.
  • the content of the (B) silane coupling agent in the polymer composition of the present invention is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the polymer. More preferably, 0.05 to 1 part by mass.
  • the organic solvent of the component (C) is not particularly limited as long as it is an organic solvent that dissolves the polymer component. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, and 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, ethylene carbonate, propylene carbonate, Dipropylene, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono
  • the polymer composition of the present invention may contain components other than the components (A) to (C).
  • examples thereof include solvents and compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the retardation material and the substrate, and the like. Not limited.
  • These poor solvents may be used alone or in combination of two or more.
  • the content thereof is preferably 5 to 80% by mass, preferably 20 to 60% by mass, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. More preferably, it is by mass.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafuck (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by DIC).
  • Examples thereof include 3M (manufactured by 3M), Asahi Guard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) and the like.
  • the content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A).
  • 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, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
  • the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition, and 1 to 20 parts by mass. Is more preferable. If the content is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive.
  • a colorless sensitizer and a triplet sensitizer are preferable.
  • Photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones, aromatic 2-hydroxys.
  • 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-methyl- ⁇ -naphthiazoline, 2- (4-biphenoyl methylene) -3-methyl- ⁇ -naphthiazolin, 2- (p-fluorobenzoyl methylene) -3 -Meth
  • aromatic 2-hydroxyketones (benzophenone), coumarin, ketocoumarin, carbonyl biscumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetal phenone ketal are preferred.
  • the polymer composition of the present invention includes a dielectric material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the retardation material as long as the effects of the present invention are not impaired.
  • a crosslinkable compound may be added for the purpose of increasing the hardness and density of the film when it is used as a conductive substance or a retardation material.
  • the polymer composition of the present invention is preferably prepared as a coating liquid so as to be suitable for forming a single-layer retardation material. That is, the polymer composition used in the present invention contains the components (A) and (B), the above-mentioned solvent or compound that improves the film thickness uniformity and surface smoothness, and the adhesion between the liquid crystal alignment film and the substrate. It is preferable that a compound or the like for improving the above is prepared as a solution dissolved in the organic solvent of the component (C).
  • the content of the component (A) is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass in the composition of the present invention.
  • the polymer composition of the present invention may contain other polymers in addition to the polymer of the component (A) as long as the liquid crystal expression ability and the photosensitive performance are not impaired.
  • the content of the other polymer in the polymer component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass.
  • 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 single-layer retardation material of the present invention can be produced by a method including the following steps (I) to (III).
  • Step (I) is a step of applying the composition of the present invention onto a substrate to form a coating film. More specifically, the composition of the present invention is coated on a substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal (for example, aluminum, molybdenum, chromium, etc.)), glass substrate, quartz substrate. , ITO substrate, etc.) and films (for example, resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.), bar coat, spin coat, flow coat, roll coat, etc.
  • TAC triacetyl cellulose
  • the solvent can be evaporated at 50 to 200 ° C., preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven to obtain a coating film.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven to obtain a coating film.
  • 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 ultraviolet rays having a wavelength in the range of 100 to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of coating film 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 rays for example, light emitted from a high-pressure mercury lamp can be used.
  • the irradiation amount of polarized ultraviolet rays depends on the coating film used.
  • the irradiation amount is 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 within the range of 1 to 50%, and more preferably within the range of 1 to 50%.
  • step (III) the coating film irradiated with ultraviolet rays polarized in step (II) is heated. Orientation control ability can be imparted to the coating film by heating.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is exhibited.
  • the heating temperature is preferably within the temperature range of the temperature at which the polymer of the component (A) contained in the composition of the present invention exhibits liquid crystallinity (hereinafter referred to as the liquid crystal expression temperature).
  • the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when the polymer of the component (A) is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is set to a temperature 10 ° C.
  • the temperature is preferably in the range up to. 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-organization 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.
  • a temperature below the phase transition temperature (Tiso) means that the liquid crystal transition temperature at which a phase transition occurs from the solid phase to the liquid crystal phase is 130 ° C. or lower.
  • the thickness of the coating film formed after heating can be appropriately selected in consideration of the step difference of the substrate to be used and the optical and electrical properties, and is preferably 0.5 to 3 ⁇ m, for example.
  • the single-layer retardation material of the present invention thus obtained is a material having optical characteristics suitable for applications such as display devices and recording materials, and in particular, polarizing plates and retardation plates for liquid crystal displays and the like. It is suitable as an optical compensation film.
  • 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 crystal 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.
  • Example 1-1 TESOX (0.075 g) as an additive was added to the polymer solution CT1 (10.0 g), and the mixture was stirred and dissolved at room temperature for 1 hour to obtain a polymer solution T1.
  • the polymer solution T1 was used as it was as a material for forming a retardation film.
  • Example 1-2 MPMS (0.075 g) was added as an additive to the polymer solution CT1 (10.0 g) and stirred at room temperature for 1 hour to dissolve the polymer solution T2. This polymer solution T2 was used as it was as a material for forming a retardation film.
  • Example 1-3 S-1 (0.075 g) was added as an additive to the polymer solution CT1 (10.0 g), and the mixture was stirred and dissolved at room temperature for 1 hour to obtain a polymer solution T3.
  • This polymer solution T3 was used as it was as a material for forming a retardation film.
  • Example 1-4 S-2 (0.075 g) was added as an additive to the polymer solution CT1 (10.0 g), and the mixture was stirred and dissolved at room temperature for 1 hour to obtain a polymer solution T4.
  • This polymer solution T4 was used as it was as a material for forming a retardation film.
  • Example 2 As shown in Table 1, from the comparison between Example 2 and Comparative Example 2, the solution containing only polymethacrylate causes a decrease in the phase difference value due to an increase in HAZE value (whitening) due to thickening of the film.
  • the silane coupling agent of the component (B) By introducing the silane coupling agent of the component (B), the increase (whitening) of the HAZE value was significantly suppressed, and the result of maintaining a high phase difference value was obtained.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne une composition polymère contenant (A) un polymère à chaîne latérale comprenant une chaîne latérale ayant un segment photoréactif représenté par la formule (a), (B) un agent de couplage au silane, et (C) un solvant organique.
PCT/JP2020/013612 2019-03-29 2020-03-26 Composition polymère et matériau à différence de phase mono-couche WO2020203628A1 (fr)

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CN202080020046.3A CN113557265B (zh) 2019-03-29 2020-03-26 聚合物组合物及单层相位差材料
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WO2022080378A1 (fr) * 2020-10-13 2022-04-21 日産化学株式会社 Procédé de fabrication d'un matériau à différence de phase monocouche
WO2022138932A1 (fr) * 2020-12-25 2022-06-30 日産化学株式会社 Procédé de production d'un film à différence de phase monocouche et composition de polymère filmogène à différence de phase monocouche

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