WO2014073658A1 - 硬化膜を形成したフィルム、配向材および位相差材 - Google Patents
硬化膜を形成したフィルム、配向材および位相差材 Download PDFInfo
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- WO2014073658A1 WO2014073658A1 PCT/JP2013/080305 JP2013080305W WO2014073658A1 WO 2014073658 A1 WO2014073658 A1 WO 2014073658A1 JP 2013080305 W JP2013080305 W JP 2013080305W WO 2014073658 A1 WO2014073658 A1 WO 2014073658A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
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- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
Definitions
- the present invention relates to a film formed with a cured film, an alignment material, and a retardation material.
- a right-eye image is visually recognized by an observer's right eye
- a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be perceived.
- a retardation material is usually disposed on a display element such as a liquid crystal panel.
- a retardation material a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed.
- a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.
- the patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2.
- Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed.
- a solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.
- acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chains are known as usable photo-alignment materials.
- These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiating polarized UV (see Patent Documents 3 to 5). .
- an object of the present invention is an acrylic film having a cured film with excellent adhesion to a substrate on the surface, and the cured film is used as an alignment material capable of aligning a polymerizable liquid crystal with high sensitivity.
- An optical film is provided.
- Another object of the present invention is to provide a retardation material formed using an optical film provided with the alignment material.
- a first aspect of the present invention is an optical film having a cured film on an acrylic film, the cured film comprising: (A) at least one selected from the group consisting of a compound having a photoalignable group and a polymer having a photoalignable group, (B) It is related with the optical film characterized by being formed with the cured film formation composition containing the polymer which has a unit structure shown by following formula X.
- 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 an azobenzene structure group.
- the component (A) is a compound or polymer having any one of a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group in addition to a photoalignable group, and the cured film
- the forming composition further contains a cross-linking agent that reacts with component (C) (A) or component (B), or both.
- (B) in component above formula (X) it is preferred that R 1 and R 2 is a polymer having a structural unit represents a methyl group.
- the proportion of the unit structure represented by the formula (X) in the component (B) is preferably 40 to 100% by mass based on the total mass of the polymer.
- WHEREIN In the said cured film formation composition, it is preferable that content ratio of (A) component and (B) component is 5:95 thru
- the cured film is preferably used as a liquid crystal alignment film.
- a 2nd aspect of this invention is related with the liquid crystal aligning material formed using the optical film of the 1st aspect of this invention.
- the third aspect of the present invention relates to a retardation material formed using the optical film of the first aspect of the present invention.
- the first aspect of the present invention it is possible to provide an optical film having a cured film having excellent liquid crystal alignment and excellent adhesion to a substrate.
- the second aspect of the present invention it is possible to provide an alignment material having a liquid crystal alignment film excellent in liquid crystal alignment and excellent in adhesion with a substrate.
- the third aspect of the present invention it is possible to provide a phase difference material that is capable of high-precision optical patterning and excellent in adhesion to a liquid crystal alignment film formed on a substrate.
- the present inventor shows that the cured film obtained from the cured film-forming composition having a specific composition exhibits liquid crystal alignment properties that regulate liquid crystal alignment by polarized light exposure. It has been found that it can be used as an alignment material.
- the cured film obtained from the cured film formation composition which has the specific composition shows the outstanding adhesiveness between the acrylic films used as a base material. That is, the optical film of the present invention has a cured film obtained from a cured film-forming composition having a specific composition on the surface of an acrylic film, and adheres between the substrate and the cured film functioning as a liquid crystal alignment film.
- an optical film excellent in adhesiveness and further as an optical film excellent in adhesiveness with a polymerizable liquid crystal layer formed on the liquid crystal alignment film, it can be used for various optical applications.
- optical film of the present invention in which a cured film is formed will be described in detail with specific examples of components and the like.
- An optical film on which a cured film that functions as a liquid crystal alignment film is formed, and an alignment material, a retardation material, a liquid crystal display element, and the like that are formed using the optical film will be described.
- the composition forming the cured film on the surface of the optical film of the present invention contains a polymer having (A) a photo-alignment component, (B) an acrylate ester or a methacrylate ester as a unit structure. Furthermore, the composition which forms the cured film of the surface in the optical film of this invention can contain a crosslinking agent as (C) component in addition to (A) component and (B) component. Further, in addition to the (A) component, the (B) component, and the (C) component, as the (D) component, the adhesion is a compound having the (C) component, a thermally crosslinkable group, and a (meth) acryl group. Ingredients can be included. In addition to these, a crosslinking catalyst can be contained as the component (E). Furthermore, other additives can be contained as long as the effects of the present invention are not impaired. Furthermore, a solvent can be contained. Hereinafter, details of each component will be described.
- Component (A) in the cured film forming composition for forming a cured film on the surface of the optical film of the present invention is at least one selected from the group consisting of a compound having a photoalignable group and a polymer having a photoalignable group, or It is a mixture of these. That is, the component (A) is a component that imparts photoalignment to the cured film on the surface of the optical film of the present invention. In this specification, the component (A) is also referred to as a photoalignment component.
- component (A) is a low molecular weight compound
- it becomes a low molecular weight photo-alignment component as compared with the later-described polymer of the component (B) as a base.
- the component (A) when the component (A) is a low molecular weight compound, the component (A) is a compound having a photoalignment group, and further a hydroxy group, It can be set as the compound which has one group chosen from the group which consists of a carboxyl group, an amino group, and an alkoxy silyl group.
- the photo-alignment group generally refers to a functional group that exhibits the property of being aligned by light irradiation, and typically refers to a functional group at a structural site that undergoes photodimerization or photoisomerization.
- photo-alignment groups examples include a functional group that causes a photofleece rearrangement reaction (example compound: benzoate ester compound), a group that causes a photodecomposition reaction (example compound: cyclobutane ring, etc.), and the like.
- the structure part which the compound of a component can have as a photo-alignment group is the structure part which forms a dimer by light irradiation,
- a cinnamoyl group, a chalcone group, a coumarin is mentioned as the specific example. Group, anthracene group and the like. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity.
- the photoisomerizable structural site that the compound of component (A) can have as a photoalignable group refers to a structural site that changes into a cis form and a trans form by light irradiation, and specific examples thereof include an azobenzene structure. And a site comprising a stilbene structure and the like. Of these, an azobenzene structure is preferred because of its high reactivity.
- a compound having a photo-alignment group and one group selected from the group consisting of a hydroxy group, a carboxyl 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.
- X 11 is a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or a combination thereof, or a combination thereof, or through one or more bonds.
- X 12 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.
- an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to two or more groups via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
- X 13 represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group, or a phenyl group.
- X 14 represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group.
- the alkylene group having 1 to 20 carbon atoms may be branched or linear.
- X 15 represents a hydroxy group, a carboxyl group, an amino group or an alkoxysilyl group.
- X represents a single bond, an oxygen atom or a sulfur atom.
- the benzene ring when these substituents include a benzene ring, the benzene ring includes 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. It may be substituted with one or a plurality of substituents which are the same or different.
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. To 4 alkoxy groups, a halogen atom, a trifluoromethyl group or a cyano group;
- the compound having a photo-alignable group and a hydroxy group as the component (A) include, for example, compounds represented by the above formulas [A11] to [A15] and compounds other than the above 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, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic 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)
- the compound having a photo-alignable group and a carboxyl group as the component (A) include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin-3- Carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like can be mentioned.
- Specific examples of the compound having a photo-alignable group and an amino group as the component (A) include 4-aminocinnamic acid methyl ester, 4-amino cinnamic acid ethyl ester, 3-amino cinnamic acid methyl ester, Examples thereof include 3-aminocinnamic acid ethyl ester.
- Specific examples of the compound (A) having a photo-alignment group and an alkoxysilyl group include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilyl) Propyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-trimethoxy Silylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid methyl ester,
- low molecular weight photo-alignment component as component (A) can include the above-mentioned specific examples, but are not limited thereto.
- the low molecular weight photo-alignment component as the component (A) is particularly preferably a compound having a photo-alignment group and a hydroxy group.
- the compound having a photo-alignment group and a hydroxy group imparts photo-alignment to the cured film on the surface of the optical film of the present invention and improves adhesion to the polymerizable liquid crystal layer when used as an alignment material. Is particularly effective.
- the component (A) contains two or more photo-alignment groups in the molecule and / or Alternatively, a compound having two or more hydroxy groups can be used.
- a compound having two or more photo-alignable groups and two hydroxyl groups in the molecule can be used.
- compounds having two or more photoalignable groups and hydroxy groups in the molecule can be exemplified by compounds represented by the following formulae.
- the molecular weight of the low molecular weight photo-alignment component as the component (A) is controlled to a value within a desired range.
- heat curing is required. When the heating is performed, component (A) The sublimation of the low molecular weight photo-alignment component can be suppressed.
- any one of a photo-alignment group and a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group is included. It may be a mixture of multiple types of compounds.
- the component (A) is a polymer, that is, a high molecular weight polymer will be described below.
- the component (A) contained in the composition for forming the cured film on the surface of the optical film of the present invention is a high molecular weight polymer
- the component (A) is a polymer having a photoalignment group, That is, a polymer having a functional group at a structural site that undergoes photodimerization or photoisomerization as a photoalignment group, particularly an acrylic copolymer having at least a photodimerization site is preferable.
- an acrylic copolymer having one group selected from the group consisting of a hydroxy group, a carboxyl group, an amino group and an alkoxysilyl group (hereinafter also referred to as a thermal crosslinking site). It is desirable that
- the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester and styrene.
- the acrylic copolymer having a photodimerization site and a thermal crosslinking site (A) as the component may be an acrylic copolymer having such a structure.
- A photodimerization site and a thermal crosslinking site
- Examples of the photodimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred examples of the cinnamoyl group and the substituent containing a cinnamoyl structure include structures represented by the following formula [1] or [2].
- a group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the “cinnamoyl group” and the “substituent containing a cinnamoyl structure”.
- X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In that case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
- the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded in a plurality of types via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
- A represents one of formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6].
- R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 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 thermal crosslinking site is a site that is bonded to the crosslinking agent (C) by heating, and specific examples thereof include a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group, and a glycidyl group.
- the component (A) acrylic copolymer preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. On the other hand, the weight average molecular weight is less than 3,000 and is too small. In some cases, the heat resistance may cause insufficient curing, resulting in a decrease in solvent resistance or a decrease in heat resistance.
- the method for synthesizing the acrylic copolymer having a photodimerization site and a thermal crosslinking site as the component (A) is a simple method of copolymerizing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.
- Examples of the monomer having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like.
- a monomer having a cinnamoyl group is particularly preferable because of its high transparency in the visible light region and high photodimerization reactivity.
- a cinnamoyl group having a structure represented by the above formula [1] or [2] and a monomer having a substituent containing a cinnamoyl structure are more preferable.
- a monomer having a substituent containing a cinnamoyl structure are more preferable.
- it is a monomer represented by the following formula [3] or formula [4].
- X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
- the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.
- L 1 and L 2 each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
- the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
- X 3 and X 5 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring or a divalent aliphatic ring.
- the alkylene group having 1 to 20 carbon atoms may be branched or linear.
- X 4 and X 6 represent a polymerizable group.
- the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.
- A is any of Formula [A1], Formula [A2], Formula [A3], Formula [A4], Formula [A5], and Formula [A6] as described above. Represents.
- Examples of the monomer having a thermal crosslinking site 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-acryloyl Monomers having a hydroxy group such as cis-6-hydroxynorbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy
- the amount of the monomer having a photodimerization site and the monomer having a thermal crosslinking site used for obtaining the specific copolymer is determined based on the total amount of all monomers used for obtaining the specific copolymer. It is preferable that the monomer having 40% by mass to 95% by mass and the monomer having a thermal crosslinking site be 5% by mass to 60% by mass.
- the content of the monomer having a photodimerization site to 40% by mass or more, high sensitivity and good liquid crystal orientation can be imparted.
- it to 95% by mass or less sufficient thermosetting property can be imparted, and high liquid crystal orientation can be maintained with high sensitivity.
- a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group) is obtained when a specific copolymer is obtained.
- a monomer copolymerizable with the monomer (hereinafter also referred to as a monomer having a non-reactive functional group) can be used in combination.
- Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
- acrylic acid ester compounds methacrylic acid ester compounds
- maleimide compounds maleimide compounds
- acrylamide compounds acrylonitrile
- maleic anhydride maleic anhydride
- styrene compounds vinyl compounds.
- acrylic ester compound described above examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl.
- methacrylic acid ester compounds described above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl.
- Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, and 1,2-epoxy-5. Examples include hexene and 1,7-octadiene monoepoxide.
- styrene compound described above examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
- maleimide compound described above examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the method for obtaining the specific copolymer used in the composition for forming the cured film on the surface of the optical film of the present invention is not particularly limited.
- a monomer having a specific functional group a monomer having a photodimerization site and a thermal crosslinking site may be used.
- the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which has a non-reactive functional group used depending on necessity, a polymerization initiator, etc.
- Specific examples include solvents described in Solvents described below.
- the specific copolymer thus obtained is usually in the form of a solution dissolved in a solvent, and can be used as it is as the solution of the component (A) in the present invention.
- the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
- the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
- the powder of the specific copolymer may be used as it is as the component (A), or the powder may be reused in, for example, a solvent described later. You may melt
- the acrylic copolymer of component (A) may be a mixture of a plurality of types of specific copolymers.
- a low molecular weight compound or a high molecular weight specific copolymer can be used as the component (A).
- the component (A) may be a mixture of one or more low molecular weight compounds and a high molecular weight specific copolymer.
- Component (B)] (B) component contained in the composition which forms the cured film of the surface in the optical film of this invention has a unit structure derived from the methacrylic acid alkylester or acrylic acid alkylester shown by following formula X as a unit structure. It is a polymer (hereinafter also referred to as specific copolymer 2).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms.
- acrylic acid alkyl ester or methacrylic acid alkyl ester monomer as the specific monomer X examples include acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate.
- acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl methacrylate.
- methyl methacrylate is particularly preferable from the viewpoint of availability and affinity with an acrylic film used as a substrate. That is, the component (B) is a polymer obtained using methyl methacrylate as a monomer, in short, the polymer having a unit structure in which R 1 and R 2 both represent a methyl group in the formula (X) It is preferable.
- a monomer having an unsaturated double bond such as styrene is added to the specific monomer X, in addition to the acrylic acid alkyl ester and methacrylic acid alkyl ester, and these are polymerized.
- the resulting polymer can be applied.
- the composition for forming the cured film on the surface of the optical film of the present invention of the present invention may contain a crosslinking agent as the component (C) described later.
- the component (B) is at least selected from a hydroxy group, a carboxyl group, and an amino group as a substituent that can be thermally cross-linked with the component (C) in addition to the specific monomer X, which is an acrylic acid alkyl ester or a methacrylic acid alkyl ester.
- An acrylic copolymer obtained by copolymerizing a monomer having one substituent is preferable.
- a method of copolymerizing the specific monomer X and at least one monomer selected from monomers having a hydroxy group, a carboxyl group and / or an amino group is simple.
- Examples of the monomer having a hydroxy group, a carboxyl group, or an amino group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl.
- the copolymer 2 when the specific copolymer 2 is obtained, in addition to the specific monomer X and a monomer having at least one substituent selected from a hydroxy group, a carboxyl group and an amino group, the copolymer is copolymerized with the monomer. It is possible to use a monomer that is possible and does not have a substituent that can be thermally cross-linked.
- Such a monomer include an acrylic ester compound or a methacrylic ester compound having a structure different from that of the specific monomer X and a monomer having at least one substituent selected from a hydroxy group, a carboxyl group and an amino group.
- the specific example of the said monomer is given, it is not limited to these.
- the acrylate compound having a structure different from that of the specific monomer X include benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl, and the like.
- Examples of the methacrylic acid ester compound having a structure different from that of the specific monomer X include, for example, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl.
- vinyl compound examples 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.
- styrene compound examples include styrene, methyl styrene, chlorostyrene, and bromostyrene.
- maleimide compound examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the proportion of the unit structure represented by formula (X) is preferably 40% by mass to 100% by mass based on the total mass of the polymer. That is, the use amount of the specific monomer X used for obtaining the specific copolymer 2 as the component (B) is based on the total amount of all monomers used for obtaining the specific copolymer 2 as the component (B).
- the content is preferably 40% by mass to 100% by mass.
- the component (B) is at least one selected from a hydroxy group, a carboxyl group and an amino group as a substituent which can be thermally cross-linked with the component (C).
- the content is preferably 5% by mass to 30% by mass based on the total amount of all monomers used for the purpose.
- the method of obtaining the specific copolymer 2 which is an example of a component is not specifically limited,
- the solvent which coexisted the specific monomer X and the monomer other than the specific monomer X with the polymerization initiator etc. Obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C.
- the solvent used is not particularly limited as long as it dissolves the monomer represented by the above formula X, the monomer other than the monomer represented by the above formula X that is optionally used, a polymerization initiator, and the like. Specific examples are described in the section of [Solvent] described later.
- the acrylic polymer which is an example of the component (B) obtained by the above method is usually in a solution state dissolved in a solvent, and can be used as it is as the solution of the component (B) in the present invention.
- the acrylic polymer solution which is an example of the component (B) obtained by the above method, is re-precipitated by adding it to diethyl ether or water under stirring, and the generated precipitate is filtered and washed.
- the powder Under normal pressure or reduced pressure, the powder can be dried at room temperature or heated to obtain a powder of the specific copolymer 2 as the component (B).
- the polymerization initiator and unreacted monomer coexisting with the specific copolymer 2 of the component (B) can be removed, and as a result, the specific copolymer which is an example of the purified component (B) 2 powder is obtained.
- the obtained powder may be redissolved in a solvent and the above operation may be repeated.
- the specific copolymer 2 of the component (B) is used in a powder form or in a solution form in which purified powder is redissolved in a solvent described later. May be.
- the component (B) may be a mixture of plural kinds of the specific copolymer 2 shown as an example of the component (B).
- the composition for forming a cured film on the surface of the optical film of the present invention can contain a crosslinking agent as the component (C). Therefore, inside the cured film obtained from the composition for forming the cured film on the surface of the optical film of the present invention, before the photoreaction by the photo-alignment group of the compound (A), (C) a crosslinking agent A crosslinking reaction by a thermal reaction using can be performed. As a result, by using the component (C), when the cured film is used as an alignment material, it is possible to improve the resistance to the polymerizable liquid crystal applied thereon and the solvent thereof.
- the component (C) reacts with the above-described component (A) or component (B), or both of these components, and when the component (A) is a low molecular orientation component, (A) It is a crosslinking agent that reacts at a temperature lower than the sublimation temperature of the component. Moreover, when the composition which forms the cured film of the surface in the optical film of this invention contains an adhesive improvement component as (D) component mentioned later, (C) component can also react with (D) component. .
- the composition which forms the surface cured film in the film of the optical form of this Embodiment can form an orientation material with high photoreaction efficiency as above-mentioned as a cured film.
- the component (C) is preferably a hydrophilic component.
- (C) component can be disperse
- crosslinking agent (C) examples include compounds such as an epoxy compound, a methylol compound and an isocyanate compound, and a methylol compound is preferred.
- methylol compound described above examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
- alkoxymethylated glycoluril examples include, for example, 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) Examples include 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 Mitsui Cytec Co., Ltd. (currently: Nippon Cytec Industries Co., Ltd.), methylated urea resin (Trade name: UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), etc .; urea / formaldehyde system manufactured by DIC Corporation Resins (high condensation type, trade name: Becamine (registered trademark) J-300S, P-955, N) and the like.
- alkoxymethylated benzoguanamine examples include, for example, tetramethoxymethylbenzoguanamine.
- Commercially available products manufactured by Mitsui Cytec Co., Ltd. currently Nihon Cytec Industries Co., Ltd.) (trade name: Cymel (registered trademark) 1123); manufactured by Sanwa Chemical Co., Ltd. (product name: Nicalac (registered trademark) BX-) 4000, BX-37, BL-60, BX-55H) and the like.
- alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
- Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) manufactured by Mitsui Cytec Co., Ltd. (currently Nippon Cytec Industries Co., Ltd.), butoxymethyl type melamine Compound (trade name: My Coat (registered trademark) 506, 508), etc .; Methoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MW-30, MW-22, MW) manufactured by Sanwa Chemical Co., Ltd.
- it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which a hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
- a melamine compound examples thereof include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310.
- commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.) (currently: Nippon Cytec Industries Co., Ltd.). , Trade name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.) (currently: Nippon Cytec Industries Co., Ltd.), and the like.
- a hydroxymethyl group such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide or the like
- a polymer produced using an acrylamide compound or a methacrylamide compound substituted with an alkoxymethyl group can also be used.
- (Meth) acrylamide means both methacrylamide and acrylamide.
- Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
- Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
- the weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3 , 50,000 to 50,000.
- cross-linking agents can be used alone or in combination of two or more.
- the content of the crosslinking agent of component (C) in the composition for forming a cured film on the surface of the optical film of the present invention is from the compound having a photoalignable group and the polymer having a photoalignable group as component (A). It is preferably 10 to 400 parts by weight, more preferably 15 to 200 parts by weight based on 100 parts by weight of the total amount of at least one selected from the group consisting of the polymer of component (B). .
- content of a crosslinking agent is too small, the solvent tolerance and heat resistance of the cured film obtained from a cured film formation composition will fall, and the orientation sensitivity at the time of photo-alignment will fall. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be lowered.
- the composition which forms the cured film on the surface in the optical film of the present invention of the present invention comprises a compound having (C) component, a thermally crosslinkable group and a (meth) acryl group together with the (C) component (D). )
- the (meth) acryl group means both a methacryl group and an acryl group.
- the compound of component (D) enhances the adhesion between the cured polymerizable liquid crystal layer formed thereon. That is, it functions as an adhesion improving component.
- it is a compound which has a hydroxy group and a (meth) acryl group as (D) component.
- the cured film formed from the composition for forming the cured film on the surface of the optical film of the present invention containing the component (D) is used as the liquid crystal alignment film, it is formed on the liquid crystal alignment film (cured film).
- the polymerizable functional group of the polymerizable liquid crystal and the crosslinking reaction site contained in the liquid crystal alignment film can be linked by a covalent bond so as to improve the adhesion to the polymerizable liquid crystal layer.
- the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesion even under high temperature and high quality conditions, such as peeling. High durability can be exhibited.
- the content of the component (D) in the cured film forming composition of the embodiment of the present invention is at least one selected from the group consisting of a compound having a photoalignable group and a polymer having a photoalignable group as the component (A). And 100 parts by mass of the total amount of the component (B) polymer and the crosslinking agent (C), preferably 0.1 to 40 parts by mass, more preferably 5 to 35 parts by mass. Part.
- the content of the component (D) is 0.1 parts by mass or more, sufficient adhesion to the polymerizable liquid crystal layer can be imparted to the formed cured film. However, when it is more than 40 parts by mass, the storage stability of the cured film forming composition may be lowered.
- the component (D) may be a mixture of a plurality of compounds of the component (D).
- R 41 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.
- the composition for forming the cured film on the surface of the optical film of the present invention includes the components (A) and (B) described above, and further (C) component and (D) component as required.
- a crosslinking catalyst can be contained.
- As a crosslinking catalyst which is (E) component an acid or a thermal acid generator is mentioned, for example. This component (E) is effective in promoting a thermosetting reaction in the formation of a cured film using a composition for forming a cured film on the surface of the optical film of the present invention.
- the component (E) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that generates heat by pre-baking or post-baking to generate an acid, that is, a temperature of 80
- the compound is not particularly limited as long as it is a compound which generates an acid by thermal decomposition at a temperature of from 250 to 250 ° C.
- Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro.
- L-methanesulfonic acid L-methanesulfonic 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, Sulfonic acids such as 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid, or hydrates and salts thereof Is mentioned.
- Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium 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, cyanomethyl p-
- the content of the component (E) in the cured film forming composition of the embodiment of the present invention is at least one selected from the group consisting of a compound having a photoalignable group and a polymer having a photoalignable group as the component (A). , 0.01 parts by weight to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymer as component (B), the crosslinking agent as component (C), and the adhesion improving component as component (D)
- the amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 6 parts by mass.
- thermosetting and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted.
- storage stability of a cured film forming composition can be made favorable by setting it as 20 mass parts or less.
- the cured film forming composition of the embodiment of the present invention can contain other additives as long as the effects of the present invention are not impaired.
- a sensitizer can be contained.
- the sensitizer is effective in promoting the photoreaction when forming the cured film on the surface of the optical film of the present invention.
- Sensitizers include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, and nitrophenyl compounds.
- N, N-diethylaminobenzophenone which is a benzophenone derivative
- 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid which are nitrophenyl compounds, 4 -Nitrostilbene, 4-nitrobenzophenone, 5-nitroindole are particularly preferred.
- sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more compounds.
- the proportion of the sensitizer used is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 100 parts by mass of the component (A). 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance of the formed cured film may be reduced or the coating film may be roughened. There are things to do.
- the cured film forming composition according to the embodiment of the present invention includes, as other additives, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stability, as long as the effects of the present invention are not impaired. Agents, antifoaming agents, antioxidants, and the like.
- the cured film forming composition of the embodiment of the present invention is often used in a solution state dissolved in a solvent.
- the solvent used in that case is one that dissolves the component (A) and the component (B), and optionally the component (C), the component (D), the component (E), and / or other additives,
- the type and structure of the solvent are not particularly limited as long as the solvent has such solubility.
- the solvent include, for example, 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, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, ⁇ -Butyrolactone, 2-hydroxypropio Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyrolact
- solvents can be used singly 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 and methyl 3-ethoxypropionate are more preferred because of good film-forming properties and high safety.
- the composition that forms the cured film on the surface of the optical film of the present invention has a unit structure of the photo-alignment component (A) component, the methacrylic acid alkyl ester or the acrylic acid alkyl ester component (B). As a polymer dissolved in a solvent.
- the composition for forming the cured film on the surface of the optical film of the present invention further comprises a crosslinking agent as component (C), an adhesion improving component as component (D) (a compound having a hydroxy group and a (meth) acryl group) ), (E)
- a crosslinking catalyst can be contained as a component. And as long as the effect of this invention is not impaired, another additive can be contained.
- the compounding ratio (content ratio) of the component (A) and the component (B) is preferably 5:95 to 90:10 by mass ratio.
- content ratio content ratio
- the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is liable to be lowered.
- composition for forming a cured film on the surface of the optical film of the present invention are as follows.
- the blending ratio of the component (A) and the component (B) is 5:95 to 90:10 by mass ratio, and is based on 100 parts by mass of the total amount of the component (A) and the component (B).
- the blending ratio of the component (A) and the component (B) is 5:95 to 90:10 by mass ratio, and is based on 100 parts by mass of the total amount of the component (A) and the component (B).
- the blending ratio of the component (A) and the component (B) is 5:95 to 90:10 by mass ratio, and is based on 100 parts by mass of the total amount of the component (A) and the component (B). Based on 100 parts by mass of 10 parts by mass to 400 parts by mass of component (C), (A), (B) and (C), and 0.1 parts by mass to 40 parts by mass.
- D The cured film formation composition containing a component and a solvent.
- the blending ratio of the component (A) and the component (B) is 5:95 to 90:10 by mass ratio, and is based on 100 parts by mass of the total amount of the component (A) and the component (B). Based on 100 parts by mass of 10 parts by mass to 400 parts by mass of component (C), (A), (B) and (C), and 0.1 parts by mass to 40 parts by mass. Based on 100 parts by mass of the total amount of component (D), component (A), component (B), component (C) and component (D), 0.01 to 20 parts by mass of component (E) A cured film-forming composition containing a solvent.
- the blending ratio, the preparation method, and the like when the composition for forming the cured film on the surface of the optical film of the present invention is used as a solution will be described in detail below.
- the ratio of the solid content in the composition forming the cured film on the surface of the optical film of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but it is 1% by mass to 80% by mass. %, Preferably 2% to 60% by weight, more preferably 3% to 40% by weight.
- solid content means what remove
- the method for preparing the composition for forming the cured film on the surface of the optical film of the present invention is not particularly limited.
- a preparation method for example, a solution of the component (B) dissolved in the solvent is mixed with the component (A), further, the component (C), further the component (D), and the component (E) if desired. Examples thereof include a method for obtaining a uniform solution, and a method for further adding and mixing other additives as necessary at an appropriate stage of the preparation method.
- the specific copolymer (component (A)) obtained by the polymerization reaction in the solvent or the specific copolymer 2 ( The solution of (B) component) can be used as it is.
- the above-mentioned specific monomer X and heat are added to the solution of the component (A) obtained by copolymerizing the monomer having the photodimerization site, the monomer having a thermal crosslinking site and, if desired, other monomers.
- the prepared cured film-forming composition solution is preferably used for forming a cured film after being filtered using a filter having a pore size of about 0.2 ⁇ m.
- the optical film of the present invention is preferably a bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, on the acrylic film substrate with the solution of the above-mentioned cured film forming composition. It is obtained by forming a cured film by coating by printing or the like to form a coating film and then heating and drying with a hot plate or oven.
- the acrylic film the film which consists of a copolymer etc. which have a methacrylic acid alkylester and / or an acrylic acid alkylester as a main component can be used suitably.
- the acrylic film used as the substrate preferably has a thickness of 20 to 100 ⁇ m.
- a heating temperature and a heating time appropriately selected from the range of a temperature of 60 ° C. to 200 ° C. and a time of 0.4 minutes to 60 minutes are employed.
- the heating temperature and heating time are preferably 70 to 160 ° C. and 0.5 to 10 minutes.
- the thickness of the cured film on the surface of the optical film of the present invention is, for example, 0.05 ⁇ m to 5 ⁇ m, and can be appropriately selected in consideration of the level difference and optical and electrical properties of the acrylic film used as the substrate. .
- the optical film of the present invention thus produced is a compound having a liquid crystallinity including a polymerizable liquid crystal or the like using a cured film formed on a substrate as a liquid crystal alignment film by performing polarized UV irradiation.
- the optical film can be used as an alignment material.
- ultraviolet light to visible light having a wavelength of 150 nm to 450 nm is usually used, and it is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.
- the cured film serving as the liquid crystal alignment film has solvent resistance and heat resistance. Therefore, after applying a retardation material comprising a polymerizable liquid crystal solution on the alignment material, the liquid crystal The phase difference material is brought into a liquid crystal state by heating up to the phase transition temperature, and aligned on the alignment material. Then, the retardation material in a desired orientation state is cured as it is, and a retardation material having a layer having optical anisotropy can be formed.
- the retardation material for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used.
- the base material in an orientation material is an acrylic film in this invention, the phase difference material of this invention becomes useful as a phase difference film.
- the phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference characteristic.
- the patterned phase difference material used for 3D display when manufacturing the patterned phase difference material used for 3D display, it is +45 degree
- the cured film on the surface of the film can be a liquid crystal alignment film in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed, and the optical film can be used as an alignment material.
- a retardation material made of a polymerizable liquid crystal solution is applied onto the alignment material, and then heated to the phase transition temperature of the liquid crystal to bring the retardation material into a liquid crystal state.
- the polymerizable liquid crystal in a liquid crystal state is aligned on an alignment material on which two types of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region.
- the retardation material in which such an orientation state is realized is cured as it is, the above-described orientation state is fixed, and a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged. A phase difference material can be obtained.
- the optical film of the present invention can also be used as a liquid crystal alignment film of a liquid crystal display element.
- a liquid crystal display element in which liquid crystal is aligned can be manufactured. Therefore, the optical film of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.
- the number average molecular weight and weight average molecular weight of the acrylic copolymer obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran was flowed at 1 mL. It was measured under the condition that the column was eluted at a rate of 40 minutes per minute (column temperature: 40 ° C.).
- Mn number average molecular weight
- Mw weight average molecular weight
- the acrylic film used as the substrate can be produced, for example, by the following method. That is, raw material pellets made of a copolymer containing methyl methacrylate as a main component are melted by an extruder at 250 ° C., passed through a T-die, and an acrylic film having a thickness of 40 ⁇ m is produced through a casting roll and a drying roll. can do.
- Examples 1 to 12 After preparing each cured film forming composition with the composition shown in Table 1, and applying each cured film forming composition on an acrylic film using the cured film as a base material using a bar coater, a thermal circulation type at a temperature of 100 ° C. for 120 seconds. Heat drying was performed in an oven to form a cured film on the film surface, and films of Examples 1 to 12 were produced. The films of these examples were evaluated for adhesion and orientation.
- This coating film was exposed at 300 mJ / cm 2 to polymerize a polymerizable liquid crystal, and a retardation material having a polymerizable liquid crystal layer on an acrylic film was produced.
- a crosscut (1 mm ⁇ 1 mm ⁇ 100 squares) was put on the surface of the retardation material (the surface on which the polymerizable liquid crystal layer was formed) using a cutter knife, and then a cellophane tape was attached. Subsequently, when the cellophane tape was peeled off, the number of squares remaining without peeling off the polymerized liquid crystal layer on the lower cured film (liquid crystal alignment film) and further on the lower film substrate was counted.
- Example 12 and Comparative Example 3 was irradiated through a 350 ⁇ m line and space mask with 400 mJ / cm 2 perpendicular to 313 nm linearly polarized light on the surface on which the cured film was formed.
- the cured film is applied to the surface of the cured film by irradiating 313 nm linearly polarized light at 200 mJ / cm 2 perpendicularly.
- the alignment material was formed with two types of liquid crystal alignment regions whose alignment control directions differ by 90 degrees.
- a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked on a hot plate at 70 ° C. for 60 seconds.
- a 0 ⁇ m coating film was formed.
- the coating film was exposed at 300 mJ / cm 2 to polymerize the polymerizable liquid crystal, thereby preparing a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged.
- the patterned retardation material on the cured film (alignment material) formed on the prepared substrate is observed using a polarizing microscope. What was seen was evaluated as x. The evaluation results are summarized in Table 3.
- the prepared retardation material showed high adhesion to the underlying cured film and the substrate.
- the prepared alignment material exhibited liquid crystal alignment and could be subjected to optical patterning.
- Comparative Examples 1 and 2 in which the polymer having high adhesion to the base material was not used as the component (B) although optical patterning could be performed, the adhesion between the underlying cured film and the base material was poor. Met.
- Comparative Example 3 in which the component (B) was not used optical patterning could not be performed.
- the film formed with the cured film according to the present invention is very useful as a liquid crystal alignment material for a liquid crystal display element and an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display element. It is suitable as a material for forming a patterned retardation material for a 3D display. Further, a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, in particular, an interlayer insulating film and a color filter of the TFT type liquid crystal element. It is also suitable as a material for forming a protective film or an insulating film of an organic EL element.
- TFT thin film transistor
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Abstract
Description
そして、観察者がメガネを着用して3D画像を観察するディスプレイの方式の1つとしては、円偏光メガネ方式等が知られている(例えば、特許文献1を参照)。
しかしながら、上述したような従来材料から形成された光配向膜では、アクリルフィルムへの密着性が弱く、このためアクリルフィルム基材を用いて形成された高信頼のパターン化位相差材を製造することは困難であった。
したがって、アクリルフィルム基材を用いながら基材との密着性に優れる高信頼の位相差材を形成することができ、光配向技術に適用可能な配向材が求められている。
そして、本発明の別の目的は、その配向材を備える光学フィルムを用いて形成された位相差材を提供することにある。
本発明の他の目的及び利点は、以下の記載から明らかとなるであろう。
(A)光配向性基を有する化合物及び光配向性基を有するポリマーからなる群から選ばれる少なくとも一種、
(B)下記式Xで示される単位構造を有するポリマー
を含有する硬化膜形成組成物により形成されていることを特徴とする光学フィルムに関する。
本発明の第1の態様において、(A)成分の光配向性基は光二量化又は光異性化する構造の官能基であることが好ましい。
本発明の第1の態様において、(A)成分の光配向性基はシンナモイル基又はアゾベンゼン構造の基であることが好ましい。
本発明の第1の態様において、(A)成分が光配向性基のほか、ヒドロキシ基、カルボキシル基、アミノ基及びアルコキシシリル基のいずれか1つを有する化合物又はポリマーであり、そして前記硬化膜形成組成物はさらに(C)(A)成分又は(B)成分、もしくはこれら双方の成分と反応する架橋剤を含有することが好ましい。
本発明の第1の態様において、(B)成分が上記式(X)中、R1及びR2がメチル基を表す構造単位を有するポリマーであることが好ましい。
本発明の第1の態様において、(B)成分における式(X)で表される単位構造の存在割合が、該ポリマーの全質量に基いて40乃至100質量%であることが好ましい。
本発明の第1の態様において、前記硬化膜形成組成物は、(A)成分と(B)成分の含有比が質量比で5:95乃至60:40であることが好ましい。
本発明の第1の態様において、前記硬化膜形成組成物は、(A)成分及び(B)成分の合計量100質量部に基づいて、5質量部乃至400質量部の(C)成分を含有することが好ましい。
本発明の第1の態様において、前記硬化膜を液晶配向膜として用いることが好ましい。
本発明の第2の態様は、本発明の第1の態様の光学フィルムを使用して形成される液晶配向材に関する。
本発明の第3の態様は、本発明の第1の態様の光学フィルムを使用して形成される位相差材に関する。
本発明の第2の態様によれば、液晶配向性に優れ、基材との密着性に優れた液晶配向膜を有する配向材を提供することができる。
本発明の第3の態様によれば、高精度な光学パターニングが可能で、基材上に形成された液晶配向膜との密着性に優れた位相差材を提供することができる。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、(A)光配向成分、(B)アクリル酸エステル又はメタクリル酸エステルを単位構造として有するポリマーを含有する。さらに、本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、(A)成分、(B)成分に加えて、(C)成分として架橋剤を含有することができる。そして、(A)成分、(B)成分、及び(C)成分に加えて、(D)成分として、(C)成分と熱架橋可能な基と(メタ)アクリル基とを有する化合物である密着成分を含有することができる。また、これらに加えて(E)成分として架橋触媒を含有することができる。さらに、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。さらに、溶剤を含有することができる。
以下、各成分の詳細を説明する。
本発明の光学フィルムにおける表面の硬化膜を形成する硬化膜形成組成物における(A)成分は、光配向性基を有する化合物及び光配向性基を有するポリマーからなる群から選ばれる少なくとも一種、もしくはこれらの混合物である。すなわち(A)成分は、本発明の光学フィルムにおける表面の硬化膜に光配向性を付与する成分であり、本明細書において、(A)成分を光配向成分とも称する。
(A)成分が低分子量の化合物である場合、ベースとなる後述の(B)成分のポリマーに比べて低分子量の光配向成分となる。
尚、本発明において、光配向性基とは、一般に光照射によって配向する性質を発揮する官能基を指し、代表的には光二量化又は光異性化する構造部位の官能基を言う。その他の光配向性基としては、たとえば光フリース転位反応を起こす官能基(例示化合物:安息香酸エステル化合物など)、光分解反応を起こす基(例示化合物;シクロブタン環など)などが挙げられる。
X12は水素原子、ハロゲン原子、シアノ基、炭素原子数1乃至18のアルキル基、フェニル基、ビフェニル基又はシクロヘキシル基を表す。その際、炭素原子数1乃至18のアルキル基、フェニル基、ビフェニル基及びシクロヘキシル基は、共有結合、エーテル結合、エステル結合、アミド結合又は尿素結合を介して2種以上の基が結合してもよい。
X13はヒドロキシ基、メルカプト基、炭素原子数1乃至10のアルコキシ基、炭素原子数1乃至10のアルキルチオ基、フェノキシ基、ビフェニルオキシ基又はフェニル基を表す。
X14は単結合、炭素原子数1乃至20のアルキレン基、2価の芳香族環基、又は、2価の脂肪族環基を表す。ここで炭素原子数1乃至20のアルキレン基は分岐状でも直鎖状でもよい。
X15はヒドロキシ基、カルボキシル基、アミノ基又はアルコキシシリル基を表す。
Xは単結合、酸素原子又は硫黄原子を表す。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物に含有される(A)成分が高分子量の重合体である場合、(A)成分は光配向性基を有する重合体であって、すなわち光配向性基として光二量化又は光異性化する構造部位の官能基を有する重合体、特に少なくとも光二量化部位を有するアクリル共重合体であることが好ましい。さらに、光二量化部位に加え、ヒドロキシ基、カルボキシル基、アミノ基及びアルコキシシリル基からなる群から選ばれる一つの基(以下、これらの基を含めて熱架橋部位とも称する)を有するアクリル共重合体であることが望ましい。
(A)成分の光二量化部位及び熱架橋部位を有するアクリル共重合体(以下、特定共重合体とも言う。)は、斯かる構造を有するアクリル共重合体であればよく、アクリル共重合体を構成する高分子の主鎖の骨格及び側鎖の種類等について特に限定されない。
上記式[2]中、X2は水素原子、シアノ基、炭素原子数1乃至18のアルキル基、フェニル基、ビフェニル基、シクロヘキシル基を表す。その際、炭素原子数1乃至18のアルキル基、フェニル基、ビフェニル基、シクロヘキシル基は、共有結合、エーテル結合、エステル結合、アミド結合、尿素結合を介して複数種が結合してもよい。
L1及びL2は、それぞれ独立に共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。
以下、上記モノマーの具体例を挙げるが、本発明は、これらに限定されるものではない。
このようにして得られる特定共重合体は、通常、溶剤に溶解した溶液の状態であり、本発明において(A)成分の溶液としてそのまま使用することができる。
また、本実施形態においては、(A)成分のアクリル共重合体は、複数種の特定共重合体の混合物であってもよい。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物に含有される(B)成分は、単位構造として、下記式Xで示されるメタクリル酸アルキルエステル又はアクリル酸アルキルエステル由来の単位構造を有するポリマー(以下特定共重合体2ともいう)である。
以下、上記式(X)で表される繰り返し単位を与えるモノマーを、特定モノマーXと称する。
すなわち、(B)成分がメチルメタクリレートを単量体として用いて得られるポリマーであること、要するに式(X)が中、R1及びR2がいずれもメチル基を表す単位構造を有するポリマーであることが好ましい。
前記特定モノマーX等とは異なる構造を有するアクリル酸エステル化合物としては、例えば、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、グリシジルアクリレート、2,2,2-トリフルオロエチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、2-メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、2-エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、3-メトキシブチルアクリレート、2-メチル-2-アダマンチルアクリレート、2-プロピル-2-アダマンチルアクリレート、8-メチル-8-トリシクロデシルアクリレート、及び、8-エチル-8-トリシクロデシルアクリレート等が挙げられる。
すなわち、(B)成分である特定共重合体2を得るために用いられる特定モノマーXの使用量は、(B)成分である特定共重合体2を得るために用いる全モノマーの合計量に基づいて、40質量%~100質量%であることが好ましい。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、上述したように、(C)成分として、架橋剤を含有することができる。そのため、本発明の光学フィルムにおける表面の硬化膜を形成する組成物から得られた硬化膜の内部では、(A)成分の化合物の光配向性基による光反応の前に、(C)架橋剤を用いた熱反応による架橋反応を行うことができる。その結果、(C)成分を使用することにより、該硬化膜を配向材として用いられた場合に、その上に塗布される重合性液晶やその溶剤に対する耐性を向上させることができる。
また、本発明の光学フィルムにおける表面の硬化膜を形成する組成物が、後述する(D)成分として密着性向上成分を含有する場合、(C)成分は(D)成分とも反応することができる。このように(C)成分は、(A)成分の昇華温度より低温下で、(A)成分である化合物のヒドロキシ基、(D)成分である化合物のヒドロキシ基と結合する。その結果、後述するように、(A)成分及び(D)成分と、(C)成分である架橋剤とが熱反応する際に、(A)成分が昇華するのを抑制することができる。そして、本実施の光学形態のフィルムにおける表面の硬化膜を形成する組成物は、硬化膜として、上述したように、光反応効率の高い配向材を形成することができる。
本発明の本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、前記(C)成分とともに、(C)成分と熱架橋可能な基と(メタ)アクリル基とを有する化合物を(D)成分として含有することができる。なお(メタ)アクリル基とはメタクリル基とアクリル基の双方を意味する。
(D)成分の化合物は、本発明の光学フィルムにおける硬化膜を配向材として用いた場合に、その上に形成される硬化された重合性液晶の層との間の密着性を強化するように、すなわち密着性向上成分として機能する。
好ましくは、(D)成分として、ヒドロキシ基及び(メタ)アクリル基を有する化合物である。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、上述した(A)成分及び(B)成分、さらに所望により(C)成分、(D)成分に加え、さらに(E)成分として架橋触媒を含有することができる。
(E)成分である架橋触媒としては、例えば、酸又は熱酸発生剤が挙げられる。この(E)成分は、本発明の光学フィルムにおける表面の硬化膜を形成する組成物を用いた硬化膜の形成において、熱硬化反応の促進に有効となる。
本発明の実施形態の硬化膜形成組成物は、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。
その他の添加剤としては、例えば、増感剤を含有することができる。増感剤は、本発明の光学フィルムにおける表面の硬化膜を形成するに際し、その光反応を促進することにおいて有効となる。
本発明の実施形態の硬化膜形成組成物は、溶剤に溶解した溶液状態で用いられることが多い。その際に用いられる溶剤は、(A)成分及び(B)成分、所望により(C)成分、(D)成分、(E)成分、及び/又は、その他の添加剤を溶解するものであり、そのような溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、上述したように、(A)成分である光配向成分、(B)成分であるメタクリル酸アルキルエステル又はアクリル酸アルキルエステルを単位構造として有するポリマーが溶剤に溶解したものである。本発明の光学フィルムにおける表面の硬化膜を形成する組成物は、さらに、(C)成分である架橋剤、(D)成分である密着性向上成分(ヒドロキシ基及び(メタ)アクリル基を有する化合物)、(E)成分として架橋触媒を含有することができる。そして、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。
本発明の光学フィルムにおける表面の硬化膜を形成する組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、1質量%~80質量%であり、好ましくは2質量%~60質量%であり、より好ましくは3質量%~40質量%である。ここで、固形分とは、硬化膜形成組成物の全成分から溶剤を除いたものをいう。
本発明の光学フィルムは、好ましくは前述の硬化膜形成組成物の溶液をアクリルフィルム基材上に、バーコート、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布、印刷などによって塗布して塗膜を形成し、その後、ホットプレート又はオーブン等で加熱乾燥することにより、硬化膜を形成することにより得られる。
上記アクリルフィルムとしてはメタクリル酸アルキルエステル及び/又はアクリル酸アルキルエステルを主成分とした共重合体等からなるフィルムを適宜使用できる。なお基材として使用するアクリルフィルムは、その膜厚が20~100μmであることが好ましい。
そのため、本発明の光学フィルムは、各種位相差材(位相差フィルム)や液晶表示素子等の製造に好適に用いることができる。
[実施例で用いる略記号]
以下の実施例で用いる略記号の意味は、次のとおりである。
<光配向性基を有する化合物及び光配向性基を有するポリマー原料>
CIN1:4-(6-ヒドロキシヘキシルオキシ)けい皮酸メチルエステル
CIN2:4-(6-ヒドロキシヘキシルオキシ)けい皮酸メチルエステルと2-イソシアナトエチルメタクリレートとを1:1で反応させたもの
CIN3:4-(6-メタクリルオキシヘキシル-1-オキシ)けい皮酸メチルエステル
<アクリル重合体 原料>
MMA:メチルメタクリレート
HEMA:2-ヒドロキシエチルメタクリレート
THFMA:テトラヒドロフルフリルメタクリレート
BMAA:N-ブトキシメチルアクリルアミド
AIBN:α,α’-アゾビスイソブチロニトリル
<架橋剤>
HMM:ヘキサメトキシメチルメラミン
<架橋触媒>
PTSA:p-トルエンスルホン酸一水和物
<密着性向上成分>
C-1:下記の構造式で示されるヒドロキシ基及びメタクリル基を有する化合物(C1)
PM:プロピレングリコールモノメチルエーテル
PMA:プロピレングリコールモノメチルエーテルアセテート
CHN:シクロヘキサノン
CIN2 100.0g、HEMA 13.6g、重合触媒としてAIBN 1.0gをPM 443.0g、CHN 111.0gの混合溶媒に溶解し、90℃にて20時間反応させることによりアクリル共重合体溶液(固形分濃度18質量%)(P1)を得た。得られたアクリル共重合体のMnは8,900、Mwは20,200であった。
MMA 100.0g、重合触媒としてAIBN 1.0gをPM 404.0gに溶解し、80℃にて20時間反応させることによりアクリル重合体溶液(固形分濃度20質量%)(P2)を得た。得られたアクリル共重合体のMnは15,200、Mwは31,700であった。
MMA 100.0g、HEMA 11.1g、重合触媒としてAIBN 1.1gをPM 450.0gに溶解し、80℃にて20時間反応させることによりアクリル共重合体溶液(固形分濃度20質量%)(P3)を得た。得られたアクリル共重合体のMnは16,700、Mwは29,900であった。
MMA 100.0g、HEMA 11.1g、重合触媒としてAIBN 5.6gをPM 450.0gに溶解し、80℃にて20時間反応させることによりアクリル共重合体溶液(固形分濃度20質量%)(P4)を得た。得られたアクリル共重合体のMnは4,200、Mwは7,600であった。
MMA 100.0g、HEMA 42.9g、重合触媒としてAIBN 1.4gをPM 657.0gに溶解し、80℃にて20時間反応させることによりアクリル共重合体溶液(固形分濃度20質量%)(P5)を得た。得られたアクリル共重合体のMnは15,300、Mwは29,200であった。
MMA 50.0g、THFMA 40.0g、HEMA 10.0g、重合触媒としてAIBN 1.0gをPM 404.0gに溶解し、80℃にて20時間反応させることによりアクリル共重合体溶液(固形分濃度20質量%)(P6)を得た。得られたアクリル共重合体のMnは14,700、Mwは32,500であった。
HEMA 100.0g、重合触媒としてAIBN 1.0gをPM 404.0gに溶解し、80℃にて20時間反応させることによりアクリル重合体溶液(固形分濃度20質量%)(P7)を得た。得られたアクリル共重合体のMnは14,100、Mwは27,700であった。
BMAA 100.0g、重合触媒としてAIBN 4.2gをPM 193.5gに溶解し、90℃にて20時間反応させることによりアクリル重合体溶液(固形分濃度35質量%)(P8)を得た。得られたアクリル共重合体のMnは2,700、Mwは3,900であった。
CIN3 100.0g、重合触媒としてAIBN 1.0gをPMA 404.0gに溶解し、80℃にて20時間反応させることによりアクリル重合体溶液(固形分濃度20質量%)(P9)を得た。得られたアクリル共重合体のMnは7,800、Mwは21,000であった。
基材として用いるアクリルフィルムは、例えば以下の方法で作製することができる。即ち、メチルメタクリレートを主成分とした共重合体等からなる原料ペレットを250℃にて押出機で溶融、T-ダイに通過させ、キャスティングロール及び乾燥ロールなどを経て厚さ40μmのアクリルフィルムを作製することができる。
表1に示す組成にて各硬化膜形成組成物を調製し、各硬化膜形成組成物を基材として用いるアクリルフィルム上にバーコータを用いて塗布した後、温度100℃で120秒間、熱循環式オーブン中で加熱乾燥を行い、フィルム表面に硬化膜を形成し、実施例1~12のフィルムを作製した。これら実施例のフィルムについて、密着性、配向性の評価を行った。
表2に示す組成にて、各硬化膜形成組成物を調製し、実施例と同様の方法で比較例1~3のフィルムを作製した。これら比較例のフィルムについて、密着性、配向性の評価を行った。
実施例1~11及び比較例1~2のフィルムにおいて、硬化膜が形成された表面に対して、313nmの直線偏光を垂直に40mJ/cm2照射した。実施例12及び比較例3のフィルムに対しても同様に313nmの直線偏光を垂直に400mJ/cm2照射した。露光後の基材上の硬化膜の上に、水平配向用重合性液晶溶液をバーコータを用いて塗布し、次いで、70℃で60秒間ホットプレート上においてプリベークを行い、膜厚1.0μmの塗膜を形成した。この塗膜を300mJ/cm2で露光し、重合性液晶を重合させて、アクリルフィルム上に重合性液晶の層を有する位相差材を作製した。
位相差材表面(重合性液晶の層が形成された表面)にカッターナイフを用いてクロスカット(1mm×1mm×100マス)を入れ、その後、セロハンテープを貼り付けた。次いで、そのセロハンテープを剥がした時に、重合した重合性液晶の層が下層の硬化膜(液晶配向膜)並びに更に下層のフィルム基材上で剥がれず残っているマス目の個数をカウントした。重合液晶の層が剥がれず残っているマス目が90個以上残っているものを、密着性が良好であると判断○で示し、残っているマス目が90個未満の場合を密着性が不良であると判断し×で示した。得られた結果を表3にまとめて示す。
実施例1~11及び比較例1~2のフィルムに350μmのラインアンドスペースマスクを介し、硬化膜が形成された表面に対して、313nmの直線偏光を40mJ/cm2垂直に照射した。次に、マスクを取り外し、基材を90度回転させた後、硬化膜が形成された表面に対して、313nmの直線偏光を20mJ/cm2垂直に照射することにより、該硬化膜を液晶の配向制御方向が90度異なる2種類の液晶配向領域が形成された配向材とした。同様に、実施例12及び比較例3のフィルムに350μmのラインアンドスペースマスクを介し、硬化膜が形成された表面に対して、313nmの直線偏光を400mJ/cm2垂直に照射した。次に、マスクを取り外し、基材を90度回転させた後、硬化膜が形成された表面に対して、313nmの直線偏光を200mJ/cm2垂直に照射することにより、該硬化膜を液晶の配向制御方向が90度異なる2種類の液晶配向領域が形成された配向材とした。
この基材上の硬化膜(配向材)の上に、水平配向用重合性液晶溶液を、バーコータを用いて塗布し、次いで、70℃で60秒間ホットプレート上においてプリベークを行い、膜厚1.0μmの塗膜を形成した。該塗膜を300mJ/cm2で露光し、重合性液晶を重合させて、異なる位相差特性を有する2種類の領域が規則的に配列されたパターン化位相差材を作製した。
作製した基材上に形成された硬化膜(配向材)上のパターン化位相差材を、偏光顕微鏡を用いて観察し、配向欠陥なく位相差パターンが形成されているものを○、配向欠陥が見られるものを×として評価した。評価結果を表3にまとめて示す。
以上の評価を行った結果を、次の表3に示す。
一方、(B)成分に基材との密着性が高いポリマーを用いなかった比較例1及び2では、光学パターニングを行うことができたものの、下層の硬化膜並びに基材との密着性が不良であった。また、(B)成分を用いなかった比較例3では光学パターニングを行うことができなかった。
Claims (12)
- (A)成分の光配向性基が光二量化又は光異性化する構造の官能基である、請求項1に記載の光学フィルム。
- (A)成分の光配向性基がシンナモイル基である、請求項1又は請求項2に記載の光学フィルム。
- (A)成分の光配向性基がアゾベンゼン構造の基である、請求項1又は請求項2に記載の光学フィルム。
- (A)成分が光配向性基のほか、ヒドロキシ基、カルボキシル基、アミノ基及びアルコキシシリル基のうちのいずれか1つを有する化合物又はポリマーであり、そして前記硬化膜形成組成物は、さらに、
(C)(A)成分又は(B)成分、もしくはこれら双方の成分と反応する架橋剤を含有する、請求項1乃至請求項4のうちいずれか一項に記載の光学フィルム。 - (B)成分が上記式(X)中、R1及びR2がメチル基を表す構造単位を有するポリマーである、請求項1乃至請求項5のうちいずれか一項に記載の光学フィルム。
- (B)成分のポリマー中の、式(X)で表される単位構造の存在割合が、該ポリマーの全質量に基いて40乃至100質量%である、請求項1乃至請求項6のうちいずれか一項に記載の光学フィルム。
- 前記硬化膜形成組成物は、(A)成分と(B)成分の含有比が質量比で5:95乃至60:40である、請求項1乃至請求項7のいずれか一項に記載の光学フィルム。
- 前記硬化膜形成組成物は、(A)成分と(B)成分の合計量100質量部に基づいて、5質量部乃至400質量部の(C)成分を含有する、請求項5乃至請求項8のうちいずれか一項に記載の光学フィルム。
- 前記硬化膜を液晶配向膜として用いることを特徴とする、請求項1乃至請求項9のうちいずれか一項に記載の光学フィルム。
- 請求項1乃至請求項10のうちいずれか一項に記載の光学フィルムを使用して形成される液晶配向材。
- 請求項1乃至請求項10のうちいずれか一項に記載の光学フィルムを使用して形成される位相差材。
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014136889A1 (ja) * | 2013-03-08 | 2014-09-12 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JP2015229753A (ja) * | 2014-06-06 | 2015-12-21 | 大日本印刷株式会社 | 光配向性を有する熱硬化性組成物、配向層、配向層付基材、位相差板およびデバイス |
WO2016031917A1 (ja) * | 2014-08-28 | 2016-03-03 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
WO2016052490A1 (ja) * | 2014-10-01 | 2016-04-07 | Dic株式会社 | 積層体、およびそれを使用した光学フィルムまたは液晶配向膜 |
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JP2016098250A (ja) * | 2014-11-18 | 2016-05-30 | 大日本印刷株式会社 | 光配向性を有する熱硬化性組成物、配向層、配向層付基板および位相差板 |
JP2017187600A (ja) * | 2016-04-05 | 2017-10-12 | Jsr株式会社 | 液晶配向剤、保護膜形成用重合体組成物、保護膜及びその製造方法、並びに液晶素子 |
CN107615148A (zh) * | 2015-06-02 | 2018-01-19 | 日产化学工业株式会社 | 光取向用液晶取向剂、取向材料及相位差材料 |
WO2018124166A1 (ja) * | 2016-12-28 | 2018-07-05 | 日産化学工業株式会社 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102432966B1 (ko) * | 2016-09-21 | 2022-08-17 | 닛산 가가쿠 가부시키가이샤 | 경화막 형성 조성물 |
KR20200135968A (ko) * | 2018-03-27 | 2020-12-04 | 닛산 가가쿠 가부시키가이샤 | 경화막 형성 조성물, 배향재 및 위상차재 |
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JP7214397B2 (ja) * | 2018-08-23 | 2023-01-30 | 日東電工株式会社 | 偏光子、偏光フィルム、光学フィルム、ならびに画像表示装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011010635A1 (ja) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
JP2011132232A (ja) * | 2009-12-22 | 2011-07-07 | Lg Chem Ltd | 架橋性化合物及びそれを含む感光性組成物 |
WO2011126022A1 (ja) * | 2010-04-08 | 2011-10-13 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS611342A (ja) | 1984-06-14 | 1986-01-07 | Noboru Yamada | 製燻法 |
JP3767962B2 (ja) | 1997-02-19 | 2006-04-19 | シャープ株式会社 | 映像表示システム |
WO1999015576A1 (en) | 1997-09-25 | 1999-04-01 | Rolic Ag | Photocrosslinkable polyimides |
JP4161583B2 (ja) * | 2002-02-07 | 2008-10-08 | コニカミノルタホールディングス株式会社 | 偏光板の製造方法 |
JP2005049865A (ja) | 2003-07-17 | 2005-02-24 | Arisawa Mfg Co Ltd | 光学位相差素子の製造方法 |
JP2005352025A (ja) * | 2004-06-09 | 2005-12-22 | Dainippon Printing Co Ltd | 光学素子 |
JP5316740B2 (ja) | 2007-08-30 | 2013-10-16 | Jsr株式会社 | 液晶配向膜の形成方法 |
JP5498051B2 (ja) * | 2009-04-24 | 2014-05-21 | 新日鉄住金化学株式会社 | 隔壁及びカラーフィルター |
-
2013
- 2013-11-08 TW TW102140699A patent/TWI608047B/zh active
- 2013-11-08 JP JP2014545777A patent/JP6425021B2/ja active Active
- 2013-11-08 WO PCT/JP2013/080305 patent/WO2014073658A1/ja active Application Filing
- 2013-11-08 CN CN201380058113.0A patent/CN104781706B/zh active Active
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011010635A1 (ja) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
JP2011132232A (ja) * | 2009-12-22 | 2011-07-07 | Lg Chem Ltd | 架橋性化合物及びそれを含む感光性組成物 |
WO2011126022A1 (ja) * | 2010-04-08 | 2011-10-13 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
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US9823401B2 (en) | 2013-03-08 | 2017-11-21 | Nissan Chemical Industries, Ltd. | Cured film formation composition, orientation material, and retardation material |
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