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WO2025170009A1 - Composition de formation de film durci, matériau d'alignement et matériau de retard - Google Patents

Composition de formation de film durci, matériau d'alignement et matériau de retard

Info

Publication number
WO2025170009A1
WO2025170009A1 PCT/JP2025/004013 JP2025004013W WO2025170009A1 WO 2025170009 A1 WO2025170009 A1 WO 2025170009A1 JP 2025004013 W JP2025004013 W JP 2025004013W WO 2025170009 A1 WO2025170009 A1 WO 2025170009A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
cured film
component
forming composition
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/004013
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English (en)
Japanese (ja)
Inventor
直也 西村
朋哉 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of WO2025170009A1 publication Critical patent/WO2025170009A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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 cured film-forming composition that forms a cured film that aligns liquid crystal molecules, a cured film, an optical film, an alignment material, and a retardation material.
  • the present invention relates to a patterned retardation material used in 3D displays that use circularly polarized glasses, and a retardation material used in circular polarizers that are used as anti-reflection films in organic EL displays, as well as a cured film-forming composition, a cured film, an optical film, an alignment material, and a retardation material that are useful for producing the retardation material.
  • the alignment material is typically a retardation material placed on a display element that forms an image, such as a liquid crystal panel.
  • the retardation material used for this purpose has a patterned configuration in which two types of retardation regions with different retardation characteristics are regularly arranged in multiples. Note that, hereafter in this specification, such a patterned retardation material that arranges multiple retardation regions with different retardation characteristics will be referred to as a patterned retardation material.
  • Patterned retardation materials can be produced by optically patterning a retardation material made of polymerizable liquid crystals, as disclosed in Patent Document 1, for example.
  • Optical patterning of retardation materials made of polymerizable liquid crystals utilizes photo-alignment technology known for forming alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized light with different polarization directions are irradiated onto it. A photo-alignment film is then obtained as an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. A solution-like retardation material containing polymerizable liquid crystals is applied onto this photo-alignment film to achieve alignment of the polymerizable liquid crystals. The oriented polymerizable liquid crystal is then cured to form a patterned retardation material.
  • Anti-reflection coatings on organic EL displays are composed of a linear polarizer and a quarter-wave retardation plate. External light directed toward the surface of the image display panel is converted into linearly polarized light by the linear polarizer, and then converted into circularly polarized light by the subsequent quarter-wave retardation plate. This circularly polarized external light is reflected by the surface of the image display panel, but the direction of rotation of the polarization plane is reversed during this reflection. As a result, this reflected light is converted by the quarter-wave retardation plate into linearly polarized light in a direction that is blocked by the linear polarizer, in the opposite direction to when it arrived, and is then blocked by the subsequent linear polarizer, resulting in significant suppression of external emission.
  • Patent Document 2 proposes a method of constructing this optical film with reverse dispersion characteristics by combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate. With this method, an optical film with reverse dispersion characteristics can be constructed using a liquid crystal material with positive dispersion characteristics over the wide wavelength range used to display color images.
  • liquid crystal materials with reverse dispersion characteristics have been proposed as materials suitable for use in this retardation layer (Patent Documents 3 and 4).
  • liquid crystal materials with reverse dispersion characteristics instead of combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate using two retardation layers, it is possible to ensure reverse dispersion characteristics by forming the retardation layer from a single layer, thereby enabling the realization of an optical film with a simple configuration that can ensure the desired retardation over a wide wavelength band.
  • Alignment layers are used to align liquid crystals.
  • Known methods for forming alignment layers include rubbing and photo-alignment. Photo-alignment is useful because it does not generate static electricity or dust, which are problems with rubbing, and allows for quantitative control of the alignment process.
  • Acrylic resins and polyimide resins with photodimerization moieties such as cinnamoyl groups and chalcone groups in the side chains are known as photoalignment materials that can be used to form alignment materials using the photoalignment method. These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter referred to as liquid crystal alignment) when irradiated with polarized UV light (see Patent Documents 5 to 7).
  • the alignment layer In addition to being able to align liquid crystals, the alignment layer also needs to be solvent-resistant.
  • the alignment layer may be exposed to heat or solvents during the manufacturing process of the retardation material. If an alignment layer lacks solvent resistance and is exposed to solvent, its liquid crystal alignment ability may be significantly reduced.
  • Patent Document 8 proposes a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a photo-induced crosslinking reaction and a structure that crosslinks when heated, in order to obtain stable liquid crystal alignment ability, and a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a photo-induced crosslinking reaction and a compound having a structure that crosslinks when heated.
  • the alignment layer must have good adhesion to the liquid crystal layer. If the adhesion between the alignment layer and the liquid crystal layer formed on top of it is insufficient, the liquid crystal layer may peel off, for example, during the winding process when manufacturing the retardation film.
  • a cured film (alignment material) that has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, has excellent adhesion to the liquid crystal layer and acrylic film, and causes little liquid crystal repelling.
  • a cured film-forming composition that is suitable for forming a cured film (alignment material) with such properties.
  • the present invention was made based on the above findings and research results. Specifically, the object of the present invention is to provide a cured film-forming composition that uses a film such as an acrylic film as a substrate, has excellent solvent resistance, is capable of aligning polymerizable liquid crystals with high sensitivity, and can form a cured film used to form an alignment material with little repelling by baking at a low temperature of less than 100°C.
  • Another object of the present invention is to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or optical film.
  • a cured film obtained from a cured film-forming composition having a specific composition has excellent solvent resistance, is capable of aligning polymerizable liquid crystals with high sensitivity, and can be used as an alignment material that has excellent adhesion to liquid crystal layers and acrylic films and causes little repelling of liquid crystals, thereby completing the present invention.
  • the first aspect of the present invention is (A) a low molecular weight compound having a photoalignable group and a thermally crosslinkable group; (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group; (C) a polymer having 60 mol % or more of all repeating units containing a hydroxy group; (D) A polymer having 45 mol % or more of repeating units represented by the following formula (X) based on all repeating units, and also having a repeating unit having a hydroxy group: (E) inorganic fine particles whose surface has been modified with a group having no (meth)acrylic group; The present invention relates to a cured film-forming composition containing (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group, and (G) a crosslinking catalyst.
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a linear
  • the photoalignable group of the component (A) is preferably a functional group having a structure that undergoes photodimerization or photoisomerization.
  • the photoalignable group of the component (A) is preferably a cinnamoyl group or a group having an azobenzene structure.
  • the crosslinking agent (B) is preferably a polymer obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds.
  • the second aspect of the present invention relates to a cured film obtained from the cured film-forming composition of the first aspect of the present invention.
  • a third aspect of the present invention relates to an optical film having a cured film according to the second aspect of the present invention.
  • a fourth aspect of the present invention relates to an alignment material formed using the cured film of the second aspect of the present invention.
  • the fifth aspect of the present invention relates to a retardation material formed using the cured film of the second aspect of the present invention.
  • (meth)acrylic refers to both acrylic and methacrylic.
  • a cured film-forming composition which can form, by baking at a low temperature of less than 100°C, a cured film that has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, causes little liquid crystal repelling, and provides an alignment material that has excellent adhesion to a liquid crystal layer. Furthermore, according to the present invention, it is possible to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or the optical film.
  • the cured film-forming composition of the present invention will be described in detail below, citing specific examples of its components, etc. Then, the cured film and alignment material of the present invention that use the cured film-forming composition of the present invention, as well as retardation materials and liquid crystal display elements, etc., that are formed using the alignment material will be described.
  • the cured film-forming composition of the present invention contains (A) a low molecular weight compound having a photoalignable group and a thermally crosslinkable group, (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group, (C) a polymer having 60 mol % or more of all repeating units containing repeating units having a hydroxy group, (D) a polymer having 45 mol % or more of all repeating units containing repeating units represented by the above formula (X) and repeating units having a hydroxy group, (E) inorganic fine particles surface-modified with a group not containing a (meth)acrylic group, (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group, and (G) a crosslinking catalyst. Furthermore, other additives may be added as long as they do not impair the effects of the present invention. Furthermore, the cured film-forming composition of the cured film-forming composition of the
  • the component (A) in the cured film-forming composition of the present invention is a low molecular weight compound having a photoalignable group and a thermally crosslinkable group. That is, the component (A) is a component that imparts photoalignment properties to a cured film obtained from the cured film-forming composition of the present invention, and in this specification, the component (A) is also referred to as a photoalignment component.
  • the low molecular weight compound of the component (A) is a compound having a lower molecular weight than the polymer of the component (C) described below, which serves as the base for film formation in the cured film-forming composition of the present invention, and serves as a photoalignment component in the cured film-forming composition.
  • the low-molecular-weight compound of component (A) is a compound having a photoalignable group and further having a thermally crosslinkable group which is at least one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group.
  • the photoalignable group may also contain a carboxy group or an amide group.
  • photoalignable group generally refers to a functional group that exhibits the property of alignment upon irradiation with light, and typically refers to a functional group at a structural site that undergoes photodimerization or photoisomerization.
  • Other photoalignable groups include, for example, functional groups that undergo a photo-induced Fries rearrangement reaction (example compounds: benzoic acid ester compounds, etc.) and groups that undergo a photodecomposition reaction (example compounds: cyclobutane rings, etc.).
  • the photodimerizable structural moiety that the low molecular weight compound of component (A) can have as a photoalignment group is a moiety that forms a dimer upon irradiation with light, and specific examples include cinnamoyl groups, chalcone groups, coumarin groups, and anthracene groups. Of these, cinnamoyl groups are preferred due to their high transparency in the visible light region and high photodimerization reactivity.
  • a low molecular weight compound having a photoalignable group and a thermally crosslinkable group (at least one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group) is, for example, a compound represented by the following formula:
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group.
  • X11 is a structure in which 1 to 3 substituents selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof are bonded via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or a combination thereof, and a structure in which a plurality of the substituents are linked via the bond may be formed.
  • X12 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group, wherein two or more groups may be bonded to the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
  • X14 represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group, wherein the alkylene group having 1 to 20 carbon atoms may be branched or linear.
  • X 15 represents a hydroxy group, a carboxy group, an amide group, an amino group or an alkoxysilyl group, provided that when X 14 is a single bond, X 15 is a hydroxy group or an amino group.
  • X represents a single bond, an oxygen atom, or a sulfur atom, provided that when X 14 is a single bond, X is also a single bond.
  • the benzene ring may be substituted with one or more identical or different substituents selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.
  • the low molecular weight compound having a photoalignable group and a hydroxy group which is the component (A)
  • the component (A) include compounds represented by the above formulas [A11] to [A15], as well as compounds other than those formulas, such as 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester, 4-(4-hydroxybutyloxy)cinnamic acid methyl ester, 4-(3-hydroxypropyloxy)cinnamic acid methyl ester, and 4-(2-hydroxyethyloxy)cinnamic acid methyl ester.
  • ethyl ester 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid ethyl ester, 4-(4-hydroxybutyloxy)cinnamic acid ethyl ester, 4-(3-hydroxypropyloxy)cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy)cinnamic acid ethyl ester, 4-hydroxymethyloxycinnamic acid ethyl ester, 4-hydroxy hydroxycinnamic acid ethyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy)c
  • the low molecular weight compound (A) having a photoalignable group and a carboxy group include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 4-propoxycinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, and 4-(N,N-dimethylamino)cinnamic acid.
  • the low molecular weight compound having a photoalignable group and an amide group, component (A) include cinnamic acid amide, 4-methylcinnamic acid amide, 4-ethylcinnamic acid amide, 4-methoxycinnamic acid amide, and 4-ethoxycinnamic acid amide.
  • the low molecular weight compound having a photoalignable group and an alkoxysilyl group, component (A), include 4-(3-trimethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-trimethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(3-trimethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(3-triethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(3-trimethoxysilylhexyloxy)cinnamic acid ethyl ester, 4-(3-triethoxysilylhexyloxy)cinnamic acid
  • the low molecular weight compound of component (A) is preferably a compound in which a polymerizable group is bonded via a spacer to a group in which a photoalignable moiety and a thermally crosslinkable moiety are bonded, as represented by the following formula (1):
  • R 101 represents a hydroxy group, an amino group, a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group, or a bis(hydroxyalkyl)amino group
  • X 101 represents a phenylene group which may be substituted with any substituent; and the benzene ring in these definitions may be substituted with a substituent.
  • substituents include alkyl groups such as methyl, ethyl, propyl, butyl, and isobutyl; haloalkyl groups such as trifluoromethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as iodine, bromine, chlorine, and fluorine; cyano; and nitro.
  • a hydroxy group and an amino group are preferred, and a hydroxy group is particularly preferred.
  • the spacer may be a divalent group selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, and a phenylene group, or a group formed by bonding multiple such divalent groups.
  • the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by formula (1) above, and the bond between the spacer and the polymerizable group may be a single bond, an ester bond, an amide bond, a urea bond, or an ether bond.
  • the divalent groups may be the same or different, and when there are multiple bonds, the bonds may be the same or different.
  • low molecular weight compounds (A) in which a polymerizable group is bonded to a group comprising a photoalignment moiety and a thermal crosslinking moiety include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-(4-(3-methacryloxypropyl-1-oxy)acryloxy)benzoic acid, 4-(4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-methacryloxyhexyl-1-oxy)-N-(4-cyanophenyl)cinnamamide, and 4-(6-methacryloxyhexyl-1-oxy)-N-bishydroxyethylcin
  • low-molecular-weight photoalignment component (A) examples include, but are not limited to, the above.
  • a low molecular weight compound can be used as component (A).
  • Component (A) may also be a mixture of one or more low molecular weight compounds.
  • N-hydroxymethyl compounds and N-alkoxymethyl compounds include, for example, methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
  • alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde resin (high condensation type, trade name: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation (formerly Dainippon Ink and Chemicals Co., Ltd.).
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Commercially available products include those manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (product name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).
  • alkoxymethylated melamine examples include hexamethoxymethyl melamine.
  • Commercially available products include methoxymethyl-type melamine compounds (trade names: Cymel® 300, 301, 303, and 350) and butoxymethyl-type melamine compounds (trade names: Mycoat® 506 and 508) manufactured by Nihon Cytec Industries Co., Ltd.
  • compounds obtained by condensing melamine compounds, urea compounds, glycoluril compounds, and benzoguanamine compounds in which the hydrogen atoms of the amino groups have been substituted with methylol groups or alkoxymethyl groups may also be used.
  • examples include the high-molecular-weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310.
  • Commercially available melamine compounds include Cymel (registered trademark) 303
  • commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (both manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)).
  • Polymers obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds include polymers obtained by polymerizing a monomer such as N-alkoxymethyl(meth)acrylamide or N-hydroxymethyl(meth)acrylamide, either alone or copolymerized with a copolymerizable monomer.
  • polymers examples include poly(N-butoxymethylacrylamide), poly(N-ethoxymethylacrylamide), poly(N-methoxymethylacrylamide), poly(N-hydroxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-butoxymethylacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate.
  • the weight-average molecular weight of such polymers is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
  • the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard. The same applies hereinafter in this specification.
  • crosslinking agents for component (B) can be used alone or in combination of two or more.
  • the content of the crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group as component (B) is preferably 100 to 2,000 parts by mass, and more preferably 200 to 1,500 parts by mass, based on 100 parts by mass of the compound as component (A).
  • the component (C) contained in the cured film-forming composition of the present invention is a polymer (hereinafter also referred to as specific polymer C) having, as a unit structure, repeating units having a hydroxy group in an amount of 60 mol % or more of all repeating units.
  • polymer that is component (C) examples include acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamine, celluloses (cellulose or derivatives thereof), polymers with a linear or branched chain structure such as phenol novolac resins, and cyclic polymers such as cyclodextrins.
  • acrylic polymers include polymers obtained by (co)polymerizing acrylic acid esters, methacrylic acid esters, and these with monomers having unsaturated double bonds, such as styrene.
  • a simple synthesis method is to (co)polymerize a monomer having a hydroxy group and, if desired, other monomers.
  • Examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.
  • 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate are particularly preferred.
  • a monomer copolymerizable with the monomer having a hydroxy group (hereinafter also referred to as a monomer having a non-reactive functional group) can be used in combination.
  • methacrylic acid ester compounds mentioned above include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate
  • maleimide compounds mentioned above include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • styrene compounds mentioned above include styrene, methylstyrene, chlorostyrene, bromostyrene, etc.
  • vinyl compounds mentioned above include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.
  • the method for obtaining the specific polymer C used in the cured film-forming composition of the present invention is not particularly limited, but examples include a method of carrying out a polymerization reaction at a temperature of 50°C to 110°C in a solvent containing a monomer having a hydroxy group, optionally a monomer having a non-reactive functional group, a polymerization initiator, etc.
  • the solvent used in this case is not particularly limited, as long as it dissolves the monomer having a hydroxy group, optionally a monomer having a non-reactive functional group, and a polymerization initiator, etc. Specific examples include the solvents described below under [Solvent].
  • the specific polymer C obtained in this manner is usually in the form of a solution dissolved in a solvent, and can be used as is as the polymer solution of component (C) in the present invention.
  • the solution of specific polymer C obtained as described above can be reprecipitated by adding it to diethyl ether, water, or the like while stirring.
  • the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of specific polymer C.
  • This procedure makes it possible to remove the polymerization initiator and unreacted monomers that coexist with specific polymer C, resulting in a purified powder of specific polymer C. If sufficient purification cannot be achieved in one procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated.
  • the powder of the specific polymer C may be used as is as the polymer of component (C), or the powder may be redissolved in, for example, a solvent described below and used in the form of a solution.
  • the acrylic polymer an example of component (C), preferably has a weight-average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight-average molecular weight is too high, exceeding 200,000, solubility in solvents may decrease, resulting in poor handling, while if the weight-average molecular weight is too low, below 3,000, the polymer may not cure sufficiently during heat curing, resulting in poor solvent resistance and heat resistance.
  • component (C) may be a mixture of multiple types of polymers exemplified as component (C).
  • the content of component (C) in the cured film-forming composition of the present invention is 50 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, and more preferably 200 to 500 parts by mass, based on 100 parts by mass of component (A).
  • the component (D) contained in the cured film-forming composition of the present invention is a polymer (hereinafter also referred to as specific copolymer D) having repeating units represented by the following formula (X) in an amount of 45 mol % or more of all repeating units and having a repeating unit having a hydroxy group:
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a monomer that provides a repeating unit represented by the above formula (X) will be referred to as a specific monomer X.
  • Examples of specific monomer X, the alkyl acrylate or alkyl methacrylate monomer include alkyl acrylate compounds such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate, and alkyl methacrylate compounds such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.
  • alkyl acrylate compounds such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-
  • methyl methacrylate is particularly preferred in terms of availability and affinity with the acrylic film used as the substrate. That is, it is preferable that the component (D) is a polymer obtained using methyl methacrylate as a monomer, in other words, a polymer having a unit structure in which R 1 and R 2 in formula (X) both represent a methyl group.
  • Specific copolymer D, component (D) can be a polymer obtained by polymerizing specific monomer X, such as alkyl acrylate or alkyl methacrylate, as well as a monomer having an unsaturated double bond, such as styrene.
  • component (D) is preferably an acrylic copolymer obtained by copolymerizing specific monomer X, an alkyl acrylate or alkyl methacrylate, with a monomer having a hydroxy group.
  • a simple method for synthesizing an acrylic copolymer in which a monomer having a hydroxy group is further copolymerized with specific monomer X, an alkyl acrylate or alkyl methacrylate ester, is to copolymerize specific monomer X with at least one monomer selected from monomers having a hydroxy group.
  • Examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl acrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl acrylate, 10-hydroxydecyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3 -dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether me
  • 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate are particularly preferred.
  • a monomer (other monomer) that is copolymerizable with the specific monomer but does not have the crosslinkable group can be used in combination.
  • Such other monomers include specific monomer X, as well as acrylic acid ester compounds or methacrylic acid ester compounds having a structure different from that of the monomer having a hydroxy group, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
  • acrylic acid ester compounds having a structure different from that of the specific monomer X or the like include benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-
  • maleimide compound examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, allyl glycidyl ether, phenyl vinyl ether, propyl vinyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.
  • the abundance ratio of the unit structure represented by formula (X) is preferably 45 mol % to 95 mol %, more preferably 55 mol % to 90 mol %, and even more preferably 70 mol % to 90 mol %, based on the total amount of the polymer. That is, the amount of specific monomer X used to obtain specific copolymer D, which is component (D), is preferably 45 mol % to 95 mol %, more preferably 55 mol % to 90 mol %, and even more preferably 70 mol % to 90 mol %, based on the total amount of all monomers used to obtain specific copolymer D, which is component (D).
  • the total amount of hydroxyl group-containing monomers used in component (D) is preferably 5 mol % to 30 mol % based on the total amount of all monomers used to obtain specific copolymer D, which is component (D).
  • the method for obtaining specific copolymer D is not particularly limited.
  • it can be obtained by a polymerization reaction at a temperature of 50°C to 130°C in a solvent containing specific monomer X, a monomer having a hydroxy group, and optionally other monomers (other monomers), a polymerization initiator, etc.
  • the solvent used is not particularly limited, as long as it dissolves the monomer represented by formula X above, the monomer having a hydroxy group, optionally other monomers (other monomers), and the polymerization initiator, etc. Specific examples of solvents used in the polymerization reaction are described in the section below under "Solvent.”
  • the solution of the acrylic polymer, an example of component (D), obtained by the above method can be reprecipitated by pouring it into diethyl ether, water, or the like while stirring. The resulting precipitate can then be filtered and washed, and then dried at room temperature or by heating under atmospheric or reduced pressure to obtain a powder of specific copolymer D, component (D).
  • the above-mentioned procedure can remove the polymerization initiator and unreacted monomers that coexist with specific copolymer D, component (D), resulting in a purified powder of specific copolymer D, an example of component (D). If sufficient purification cannot be achieved in a single procedure, the obtained powder can be redissolved in a solvent and the above-mentioned procedure can be repeated.
  • the specific copolymer D of component (D) may be used in powder form, or in solution form in which the purified powder is redissolved in a solvent described below.
  • the component (D) may be a mixture of two or more of the specific copolymers D shown as examples of the component (D).
  • the acrylic polymer which is an example of component (D), preferably has a weight-average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight-average molecular weight is too high, exceeding 200,000, the solubility in solvents may decrease, resulting in poor handling, while if the weight-average molecular weight is too low, less than 3,000, the polymer may not cure sufficiently during heat curing, resulting in poor solvent resistance and heat resistance.
  • the content of component (D) in the cured film-forming composition of the present invention is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 200 parts by mass, based on 100 parts by mass of the low molecular weight compound having a photoalignable group and a thermally crosslinkable group (component (A)).
  • the component (E) contained in the cured film-forming composition of this embodiment is inorganic fine particles that have been surface-modified with a group that does not have a (meth)acrylic group.
  • the inorganic fine particles of component (E) include silica particles with a primary particle diameter of 1 nm to 200 nm, which are surface-modified with a group that does not have a (meth)acrylic group.
  • silica particles surface-modified with at least one silane coupling agent are preferred.
  • silica particles with a primary particle diameter of 1 nm to 100 nm or 20 nm to 100 nm that are surface-modified with a silane coupling agent are preferred.
  • the silane coupling agent used to modify the surface of the silica particles of component (E) of the cured film-forming composition of the present invention may be one that does not have a (meth)acrylic group, and examples thereof include methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, cyclopentyltrimethoxysilane, n-hexyltrimethoxysilane, cyclohexyltrimethoxysilane, isooctyltrimethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, benzyltrimethoxysilane, 1-naphthyltrime
  • Silane coupling agents can be used alone or in combination of two or more.
  • the amount of the silane coupling agent used is preferably 0.1 to 2.0 mmol, more preferably 0.5 to 2.0 mmol, and even more preferably 0.5 to 1.7 mmol, per 1 g of silica particles.
  • the affinity and adhesion between the surface of the silica particles and the organic resin are sufficient, the transmittance of the cured product and molded article obtained from the cured film-forming composition of the present invention does not decrease, and cracks can be prevented from occurring at the base of the cured product and molded article after the development process using an organic solvent.
  • an amount of silane coupling agent less than 2.0 millimoles the silane coupling agent does not become excessive relative to the silica particles, and no silane coupling agent is left unused in the surface modification of the silica particles, allowing the storage stability and mechanical properties of the cured product and molded article to be maintained.
  • the silica particles of component (E) have a primary particle diameter of, for example, 1 nm to 200 nm.
  • primary particles are particles that make up the powder, and particles formed by agglomeration of these primary particles are called secondary particles.
  • the primary particle diameter calculated from this relationship is the average particle diameter, which is the diameter of the primary particles.
  • Using particles with a primary particle diameter greater than 1 nm can suppress silica particle aggregation and improve storage stability.
  • Using particles with a primary particle diameter smaller than 200 nm can improve the transparency of the cured product and molded article.
  • the silica particles of component (E) can be obtained by reacting surface-unmodified silica particles with the silane coupling agent using any of a variety of known methods.
  • the surface-unmodified silica particles in the form of a dispersion of the silica particles in an organic solvent (organosilica sol).
  • the organosilica sol may be a commercially available water-dispersed silica sol in which the water is replaced with an organic solvent using known methods such as reduced pressure distillation or ultrafiltration, or a commercially available powdered silica particle dispersed in an organic solvent.
  • the silica solids concentration in the organosilica sol is not particularly limited, but is generally preferably 60% by mass or less.
  • the content of component (E) in the cured film-forming composition of the present invention is preferably 3 to 60 parts by mass, more preferably 3 to 45 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total amount of components (A), (B), (C), (D), and (F) described below contained in the cured film-forming composition. If the content of component (E) is less than 3 parts by mass, the heat resistance of the cured product and molded article obtained from the cured film-forming composition may be deteriorated. If the content of component (E) is more than 60 parts by mass, haze may occur in the cured product and molded article, and the transmittance may be reduced.
  • the component (E) may be used singly or in combination of two or more. For example, multiple silica particles with different primary particle sizes may be combined, or multiple silica particles with different types and amounts of silane coupling agent used for surface modification may be combined.
  • Component (F) The component (F) contained in the cured film-forming composition of the present embodiment is a compound having a hydroxy group and a (meth)acrylic group.
  • the compound of component (F) preferably has one or more hydroxy groups and one or more (meth)acrylic groups.
  • the polymerizable functional groups of the polymerizable liquid crystal and the cross-linking reaction sites of the alignment material can be covalently linked to improve adhesion between the alignment material and the polymerizable liquid crystal layer.
  • the retardation material of this embodiment which is formed by laminating cured polymerizable liquid crystal on the alignment material of this embodiment, can maintain strong adhesion even under high-temperature and high-humidity conditions and exhibit high durability against peeling, etc.
  • the content of component (F) in the cured film-forming composition of this embodiment is preferably 1 to 150 parts by mass, and more preferably 1 to 70 parts by mass, based on 100 parts by mass of the low molecular weight compound having a photoalignable group and a thermally crosslinkable group, which is component (A).
  • component (F) may be a mixture of multiple types of compounds of component (F).
  • R 111 represents a hydrogen atom or a methyl group
  • s represents an integer of 1 to 10
  • m, n, o, p, q, and r each independently represent an integer of 0 to 6.
  • the cured film-forming composition of the present invention further contains a crosslinking catalyst as a component (G) in addition to the above-described components (A), (B), (C), (D), (E), and (F).
  • the crosslinking catalyst component (G) can be, for example, an acid or a thermal acid generator.
  • Component (G) is effective in accelerating the thermal curing reaction when forming a cured film from the cured film-forming composition of the present invention (i.e., the composition that forms the cured film on the surface of the optical film of the present invention, as described below).
  • component (G) is not particularly limited as long as it is a sulfonic acid group-containing compound, hydrochloric acid or its salt, or a compound that generates an acid upon thermal decomposition during pre-baking or post-baking, i.e., a compound that generates an acid upon thermal decomposition at a temperature of 60°C to 250°C.
  • Such compounds include, for example, sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, non
  • examples of compounds that generate acid when heated (by thermal decomposition) include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester,
  • the (G) component is commercially available, and examples include TA-100, TA-100FG, IK-1, and IK-1FG (all manufactured by San-Apro Co., Ltd.), San-Aid (registered trademark) SI-B2A, San-Aid (registered trademark) SI-B7, San-Aid (registered trademark) SI-B3A, San-Aid (registered trademark) SI-B3, San-Aid (registered trademark) SI-B5, San-Aid (registered trademark) SI-B4, San-Aid (registered trademark) SI-150, San-Aid (registered trademark) SI-110, San-Aid (registered trademark) SI-60, San-Aid (registered trademark) SI-80, and San-Aid (registered trademark) SI-100 (all manufactured by Sanshin Chemical Industry Co., Ltd.).
  • the content of component (G) in the cured film-forming composition of the present invention is preferably 0.01 to 100 parts by weight, more preferably 1 to 100 parts by weight, even more preferably 10 to 100 parts by weight, and particularly preferably 20 to 80 parts by weight, per 100 parts by weight of component (A).
  • the content of component (G) is 0.01 parts by weight or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light exposure can also be imparted.
  • the storage stability of the cured film-forming composition can be improved.
  • the cured film-forming composition according to an embodiment of the present invention may contain other additives as long as the effects of the present invention are not impaired.
  • Other additives that may be included include, for example, a sensitizer, which is effective in accelerating the photoreaction when forming a cured film on the surface of the optical film of the present invention.
  • Sensitizers include derivatives of benzophenone, anthracene, anthraquinone, and thioxanthone, as well as nitrophenyl compounds.
  • benzophenone derivative N,N-diethylaminobenzophenone and the nitrophenyl compounds 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole are particularly preferred.
  • sensitizers are not limited to those specifically mentioned above. They can be used alone or in combination of two or more compounds.
  • the proportion used is preferably 1 to 100 parts by mass, and more preferably 10 to 80 parts by mass, per 100 parts by mass of component (A). If this proportion is too small, the effect of the sensitizer may not be fully achieved, and if it is too large, the transmittance of the cured film formed may decrease, or the coating film may become rough.
  • the cured film-forming composition of this embodiment of the present invention may contain other additives such as silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, and antioxidants, as long as the effects of the present invention are not impaired.
  • the cured film-forming composition according to the embodiment of the present invention can be used in the form of a solution dissolved in a solvent.
  • the solvent used in this case is one that dissolves the components (A), (B), (C), (D), (E), (F), and (G), and, if necessary, other additives, and the type and structure of the solvent are not particularly limited as long as it has the ability to dissolve the components.
  • solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone,
  • suitable solvents include acetone, ⁇ -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl
  • Solvents are commercially available, and examples include Neoethanol (registered trademark) PM, Neoethanol (registered trademark) MIP, Neoethanol (registered trademark) IPM, Neoethanol (registered trademark) IPE, Neoethanol (registered trademark) PHI, Neoethanol (registered trademark) MHI, Neoethanol (registered trademark) PIP, Neoethanol (registered trademark) HIMTE, Neoethanol (registered trademark) PHM, Neoethanol (registered trademark) IPME, and Neoethanol (registered trademark) P-7 (all manufactured by Taishin Chemical Co., Ltd.).
  • solvents can be used alone or in combination of two or more.
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and Neoethanol (registered trademark) IPM are more preferred due to their excellent film-forming properties and high safety.
  • the cured film-forming composition of the present invention (i.e., the composition that forms the cured film on the surface of the optical film of the present invention) comprises, as described above, component (A) a low molecular weight compound having a photoalignment group and a thermally crosslinkable group (photoalignment component), component (B) a crosslinker having an N-hydroxymethyl group or an N-alkoxymethyl group, component (C) a polymer having 60 mol % or more of all repeating units containing repeating units having a hydroxy group, component (D) a polymer having 45 mol % or more of all repeating units of repeating units represented by formula (X) and having repeating units containing a hydroxy group, component (E) inorganic fine particles that are surface-modified with a group that does not contain a (meth)acrylic group, component (F) a low molecular weight compound having both a (meth)acrylic group and
  • Preferred examples of the cured film-forming composition of the present invention are as follows:
  • a cured film-forming composition comprising: component (A); 100 to 2,000 parts by weight of component (B) based on 100 parts by weight of the compound that is component (A); 50 to 1,500 parts by weight of component (C) based on 100 parts by weight of component (A); 10 to 500 parts by weight of component (D) based on 100 parts by weight of the low molecular weight compound that has a photoalignable group and a thermally crosslinkable group that is component (A); 3 to 60 parts by weight of component (E) based on 100 parts by weight of the total of components (A), (B), (C), (D), and (F); 1 to 150 parts by weight of component (F) based on 100 parts by weight of component (A); 0.01 to 100 parts by weight of component (G) based on 100 parts by weight of component (A); and a solvent.
  • the blending ratios, preparation method, etc. when the cured film-forming composition of the present invention is used as a solution (so-called varnish) will be described in detail below.
  • the solid content of the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is preferably 1 to 80% by mass, more preferably 2 to 60% by mass, and even more preferably 3 to 40% by mass.
  • the solid content refers to all components of the cured film-forming composition excluding the solvent.
  • the method for preparing the cured film-forming composition of the present invention is not particularly limited.
  • preparation methods include mixing components (A), (B), (C), (E), (F), and (G) in a predetermined ratio with a solution of component (D) dissolved in a solvent to form a homogeneous solution, or adding and mixing other additives as needed at an appropriate stage in this preparation method.
  • component (G) may be added immediately before use to enhance the storage stability of the varnish.
  • the solution of specific copolymer D (component (D)) obtained by polymerization in a solvent can be used as is.
  • components (A), (B), (C), (E), (F), etc. are added to a solution of component (D) obtained by copolymerizing the aforementioned monomer having a hydroxy group, monomer X, and, if desired, other monomers to form a homogeneous solution.
  • additional solvent may be added to adjust the concentration.
  • the solvent used in the production process of component (D) and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.
  • the optical film of the present invention is preferably obtained by applying the above-mentioned cured film-forming composition (a solution thereof) onto a film (for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) substrate by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, printing, or the like to form a coating film, and then heating and drying the coating on a hot plate, in an oven, or the like to form a cured film.
  • a film for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film
  • acrylic film a film made of a copolymer whose main monomer component is alkyl methacrylate ester and/or alkyl acrylate ester can be used as appropriate.
  • Polarized UV irradiation typically uses ultraviolet to visible light with wavelengths between 150 nm and 450 nm, and is performed by irradiating the material with linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.
  • the cured film that becomes the liquid crystal alignment film is solvent-resistant and heat-resistant. Therefore, after applying a retardation material made of a polymerizable liquid crystal solution onto this alignment material, the retardation material can be converted to a liquid crystal state by heating it to the phase transition temperature of the liquid crystal, and then oriented on the alignment material. Then, by curing the retardation material in the desired alignment state, a retardation material with a layer having optical anisotropy can be formed.
  • liquid crystal monomers having polymerizable groups and compositions containing them are used as retardation materials.
  • the substrate of the alignment material is a film, so the retardation material of the present invention is useful as a retardation film.
  • Retardation materials that form such retardation materials are in a liquid crystal state and can assume orientation states such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment on the alignment material, and each can be used depending on the required retardation characteristics.
  • the cured film on the surface of the optical film of the present invention is exposed to polarized UV light through a line-and-space pattern mask at an angle of, for example, +45 degrees from a predetermined reference.
  • the mask is then removed and the cured film is exposed to polarized UV light at an angle of -45 degrees with a smaller exposure dose.
  • a retardation material made of a polymerizable liquid crystal solution is then applied to the alignment material, and the retardation material is then placed in a liquid crystal state by heating to the liquid crystal phase transition temperature.
  • the polymerizable liquid crystal in the liquid crystal state is oriented on the alignment material with the two types of liquid crystal alignment domains formed, forming alignment states corresponding to each liquid crystal alignment domain.
  • the retardation material with this alignment state is then cured as is to fix the above-mentioned alignment state, thereby obtaining a patterned retardation material with two types of retardation domains with different retardation characteristics, each arranged in a regular pattern.
  • the optical film of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element.
  • the optical film of the present embodiment formed as described above can be used to manufacture a liquid crystal display element in which the liquid crystal is aligned by laminating two optical films together via a spacer so that the alignment materials of the two optical films face each other, and then injecting liquid crystal between the substrates. Therefore, the optical film of the present invention can be suitably used in the production of various retardation materials (retardation films), liquid crystal display elements, and the like.
  • BMAA N-butoxymethylacrylamide 4HBA: 4-hydroxybutyl acrylate MMA: methyl methacrylate
  • AIBN ⁇ , ⁇ '-azobisisobutyronitrile
  • MAIB 2,2'-azobis(isobutyrate) dimethyl
  • ⁇ (G) component crosslinking catalyst>
  • CSA ( ⁇ )-10-camphorsulfonic acid
  • ⁇ Preparation of Composition> ⁇ Preparation Example 1> (A) component M6CA (0.080 g), (B) component 30 mass% PM solution of the acrylic polymer obtained in Synthesis Example 1 (PB-1) (1.093 g), (C) component 40 mass% PM solution of the acrylic polymer obtained in Synthesis Example 2 (PC-1) (0.520 g), (D) component 20 mass% PM solution of the acrylic copolymer obtained in Synthesis Example 3 (PD-1) (0.400 g), (E) component E-1 (0.267 g), (F) component PE-200 (0.024 g), and PM (7.614 g) were added, stirred for 2 hours, and dissolution was confirmed visually. Thereafter, by filtration through a glass filter having a pore size of 1.0 ⁇ m, a composition (A-1) having a solids concentration of 8.0 mass% was prepared.
  • Omnirad registered trademark
  • IGM Resins BV formerly BA
  • Example 1-1 A-1 (2.00 g) obtained in Preparation Example 1, G-1 (0.08 g) obtained in Preparation Example 10, EA (0.90 g) as a dilution solvent, and IPM (0.90 g) were added and stirred for 15 hours to obtain a cured film-forming composition (AL-1).
  • Examples 1-2 to 1-4 Cured film-forming compositions (AL-2) to (AL-4) were obtained in the same manner as in Example 1-1, except that A-2 to A-4 were used instead of A-1.
  • Example 2-1> The cured film-forming composition (AL-1) obtained in Example 1-1 was applied to an acrylic film substrate using a bar coater to a wet film thickness of 6 ⁇ m. Heat drying was performed in a heat circulation oven at 90°C for 1 minute to form a cured film on the film. The surface of this cured film was then irradiated vertically with linearly polarized light having a wavelength of 313 nm at an exposure dose of 20 mJ/ cm2 to form a liquid crystal alignment film.
  • Example 2-1 to 2-5 The same procedure as in Example 2-1 was carried out except that AL-2 to AL-4 or CL-1 to CL-5 were used instead of the cured film-forming composition AL-1, to produce retardation films (S-2) to (S-4) and (R-1) to (R-5), as shown in the table below.
  • component (E) By using inorganic fine particles that have been surface-modified with groups that do not have (meth)acrylic groups as component (E), interaction with component (F), a low molecular weight compound that has both (meth)acrylic groups and hydroxyl groups, is suppressed, resulting in component (F) being ubiquitous on the surface and not hindering its function as an adhesion promoter, and it is thought that an alignment material with high adhesion to the liquid crystal layer can be obtained.
  • component (F) By using inorganic fine particles that have been surface-modified with groups that do not have (meth)acrylic groups as component (E), interaction with component (F), a low molecular weight compound that has both (meth)acrylic groups and hydroxyl groups, is suppressed, resulting in component (F) being ubiquitous on the surface and not hindering its function as an adhesion promoter, and it is thought that an alignment material with high adhesion to the liquid crystal layer can be obtained.
  • Films formed with the cured film of the present invention are extremely useful as liquid crystal alignment materials for liquid crystal display elements, and as alignment materials for forming optically anisotropic films provided inside or outside liquid crystal display elements, and are particularly suitable as materials for forming patterned retardation materials for 3D displays. Furthermore, they are also suitable as materials for forming cured films such as protective films, planarizing films, and insulating films in various displays such as thin-film transistor (TFT) liquid crystal display elements and organic EL elements, and are particularly suitable as materials for forming interlayer insulating films in TFT liquid crystal elements, protective films for color filters, or insulating films in organic EL elements.
  • TFT thin-film transistor

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

Le problème décrit par la présente invention est de fournir une composition de formation de film durci qui implique l'utilisation d'un film tel qu'un film acrylique en tant que matériau de base, présente une excellente résistance aux solvants, est capable d'aligner un cristal liquide polymérisable avec une sensibilité élevée, et est destinée à former un film durci utilisé pour former un matériau d'alignement avec peu de rétraction par cuisson à basse température à moins de 100 °C. La solution de l'invention concerne une composition de formation de film durci contenant (A) un composé à faible poids moléculaire ayant un groupe photo-alignable et un groupe thermiquement réticulable, (B) un agent de réticulation ayant un groupe N-hydroxyméthyle ou un groupe N-alcoxyméthyle, (C) un polymère dans lequel 60 % en moles ou plus des motifs de répétition totaux comprennent un groupe hydroxyle, (D) un polymère qui a un motif de répétition ayant un groupe hydroxyle et dans lequel un motif de répétition représenté par la formule (X) représente 45 % en moles ou plus des motifs de répétition totaux, (E) des particules fines inorganiques modifiées en surface par un groupe n'ayant pas de groupes (méth)acryliques, (F) un composé à faible poids moléculaire ayant à la fois un groupe (méth)acrylique et un groupe hydroxy, et (G) un catalyseur de réticulation. (Dans la formule, R1 représente un atome d'hydrogène ou un groupe méthyle, et R2 représente un groupe alkyle linéaire ou ramifié ayant de 1 à 5 atomes de carbone.)
PCT/JP2025/004013 2024-02-07 2025-02-06 Composition de formation de film durci, matériau d'alignement et matériau de retard Pending WO2025170009A1 (fr)

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JP2024017312 2024-02-07

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026416A (ja) * 1999-07-12 2001-01-30 Kansai Research Institute 粒子分散体
KR20040093580A (ko) * 2003-04-30 2004-11-06 (주)애드뷰 실리카를 포함하는 액정 배향제 조성물, 이를 이용한 액정배향막, 그 제조방법 및 상기 액정 배향막을 포함하는액정 소자
WO2013054784A1 (fr) * 2011-10-11 2013-04-18 日産化学工業株式会社 Composition formant un film durci, matériau d'orientation, et matériau de déphasage
WO2014010688A1 (fr) * 2012-07-12 2014-01-16 日産化学工業株式会社 Composition de formation de film durci, matière d'alignement et matière de déphasage
WO2014065324A1 (fr) * 2012-10-24 2014-05-01 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de déphasage
JP2015026050A (ja) * 2013-06-18 2015-02-05 Jsr株式会社 液晶配向剤、位相差フィルム及び位相差フィルムの製造方法
WO2015030000A1 (fr) * 2013-08-27 2015-03-05 日産化学工業株式会社 Composition permettant de former un film durci, matériau d'alignement, et matériau à différence de phase
WO2015129890A1 (fr) * 2014-02-28 2015-09-03 日産化学工業株式会社 Composition pour formation de film dur, matériau d'orientation, et matériau de déphasage
WO2016143865A1 (fr) * 2015-03-11 2016-09-15 日産化学工業株式会社 Composition formant un film durci, matériau d'alignement et matériau de différence de phase
WO2017069252A1 (fr) * 2015-10-23 2017-04-27 富士フイルム株式会社 Composition pour films de photoalignement, film de photoalignement, stratifié optique et dispositif d'affichage d'image
US20200310200A1 (en) * 2019-03-29 2020-10-01 Sharp Kabushiki Kaisha Photo-alignment film, retardation substrate, liquid crystal display device, and method for producing photo-alignment film

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026416A (ja) * 1999-07-12 2001-01-30 Kansai Research Institute 粒子分散体
KR20040093580A (ko) * 2003-04-30 2004-11-06 (주)애드뷰 실리카를 포함하는 액정 배향제 조성물, 이를 이용한 액정배향막, 그 제조방법 및 상기 액정 배향막을 포함하는액정 소자
WO2013054784A1 (fr) * 2011-10-11 2013-04-18 日産化学工業株式会社 Composition formant un film durci, matériau d'orientation, et matériau de déphasage
WO2014010688A1 (fr) * 2012-07-12 2014-01-16 日産化学工業株式会社 Composition de formation de film durci, matière d'alignement et matière de déphasage
WO2014065324A1 (fr) * 2012-10-24 2014-05-01 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de déphasage
JP2015026050A (ja) * 2013-06-18 2015-02-05 Jsr株式会社 液晶配向剤、位相差フィルム及び位相差フィルムの製造方法
WO2015030000A1 (fr) * 2013-08-27 2015-03-05 日産化学工業株式会社 Composition permettant de former un film durci, matériau d'alignement, et matériau à différence de phase
WO2015129890A1 (fr) * 2014-02-28 2015-09-03 日産化学工業株式会社 Composition pour formation de film dur, matériau d'orientation, et matériau de déphasage
WO2016143865A1 (fr) * 2015-03-11 2016-09-15 日産化学工業株式会社 Composition formant un film durci, matériau d'alignement et matériau de différence de phase
WO2017069252A1 (fr) * 2015-10-23 2017-04-27 富士フイルム株式会社 Composition pour films de photoalignement, film de photoalignement, stratifié optique et dispositif d'affichage d'image
US20200310200A1 (en) * 2019-03-29 2020-10-01 Sharp Kabushiki Kaisha Photo-alignment film, retardation substrate, liquid crystal display device, and method for producing photo-alignment film

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