WO2020080359A1 - 積層体および画像表示装置 - Google Patents
積層体および画像表示装置 Download PDFInfo
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- WO2020080359A1 WO2020080359A1 PCT/JP2019/040495 JP2019040495W WO2020080359A1 WO 2020080359 A1 WO2020080359 A1 WO 2020080359A1 JP 2019040495 W JP2019040495 W JP 2019040495W WO 2020080359 A1 WO2020080359 A1 WO 2020080359A1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Images
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
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- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
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- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/55—Liquid crystals
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
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- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2401/00—Presence of cellulose
- C09J2401/006—Presence of cellulose in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
- C09J2429/003—Presence of polyvinyl alcohol in the primer coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/003—Presence of (meth)acrylic polymer in the primer coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
Definitions
- the present invention relates to a laminate and an image display device.
- a liquid crystal cured film, a pressure-sensitive adhesive layer, a retardation film, a pressure-sensitive adhesive layer is a circularly polarizing plate laminated in this order, the liquid crystal cured film,
- the present invention provides a laminate having a support, an alignment layer and a light absorption anisotropic layer, in which only the support can be easily peeled off, and an image display device using the same. This is an issue.
- the present inventors have found that the peelability at other interfaces changes depending on the properties of the pressure-sensitive adhesive layer when it is bonded to another member. That is, in a laminate having a support, an alignment layer, a light absorption anisotropic layer and an adhesive layer in this order, and having a thickness of 5 ⁇ m or less between the support and the support-free adhesive layer and the adhesive layer, It has been found that by setting the thickness of the adhesive layer to a specific value, it is possible to provide a laminate in which only the support can be easily peeled off.
- the thickness from the support not including the support and the adhesive layer to the adhesive layer is 5 ⁇ m or less, The thickness of the adhesive layer is 5 ⁇ m to 50 ⁇ m,
- the alignment layer is a photo-alignment layer formed using a composition for forming an alignment layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.
- the adhesive layer has a storage elastic modulus of 100 kPa to 20 MPa.
- the cinnamoyl compound has a repeating unit A containing a photoalignable group represented by the formula (A) described below and a repeating unit B containing a crosslinkable group represented by the formula (B) described below,
- L 1 in the formula (A) described below is a divalent linking group represented by any of the formulas (1) to (10) described below.
- the laminate according to [5], wherein the liquid crystal compound is a polymerizable liquid crystal compound.
- the laminate according to [5], wherein the liquid crystal compound is a polymer liquid crystal compound.
- a laminate having a support, an alignment layer and a light absorption anisotropic layer, in which only the support can be easily peeled off, and an image display device using the same are provided. be able to.
- a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.
- parallel and orthogonal do not mean parallel and orthogonal in a strict sense, but mean a range of ⁇ 5 ° from parallel or orthogonal.
- each component a substance corresponding to each component may be used alone or in combination of two or more.
- the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
- “(meth) acrylate” is a notation representing “acrylate” or “methacrylate”
- (meth) acryl” is a notation representing “acryl” or “methacryl”
- “(Meth) acryloyl” is a notation that represents “acryloyl” or “methacryloyl”.
- the liquid crystal composition and the liquid crystal compound also include, as a concept, those that no longer exhibit liquid crystallinity due to curing or the like.
- the laminate of the present invention is a laminate having a support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer in this order. Further, in the laminate of the present invention, the thickness between the support not including the support and the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is 5 ⁇ m or less, and the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m to 50 ⁇ m. Furthermore, the laminate of the present invention is a photo-alignment layer in which the alignment layer is formed by using the composition for forming an alignment layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.
- the laminated body 10 shown in FIG. 1 has a support 1, an alignment layer 2, a light absorption anisotropic layer 3, and an adhesive layer 4 in this order. Further, the laminated body 10 has a thickness between the support 1 and the adhesive layer 4 which does not include the support 1 and the adhesive layer 4, that is, from the surface of the support 1 on the side of the alignment layer 2 to the anisotropic light absorption of the adhesive layer 4.
- the distance to the surface on the side of the functional layer 3 is 5 ⁇ m or less, preferably 1 ⁇ m to 4 ⁇ m. Further, in the laminate 10, the thickness of the adhesive layer 4 is 5 ⁇ m to 50 ⁇ m.
- the support 1 and the alignment layer 2 are in contact with each other. Further, in the laminate of the present invention, as shown in FIG. 1, the alignment layer 2 and the light absorption anisotropic layer 3 are preferably in contact with each other.
- the laminate of the present invention preferably further has a cured layer 5 having a thickness of 100 nm or less between the light absorption anisotropic layer 3 and the adhesive layer 4.
- the laminate of the present invention further comprises a layer containing a polyvinyl alcohol resin having a thickness of 2 ⁇ m or less between the light absorption anisotropic layer 3 and the adhesive layer 4 (hereinafter, also referred to as “PVA layer”). Abbreviated) 6.
- PVA layer a polyvinyl alcohol resin having a thickness of 2 ⁇ m or less between the light absorption anisotropic layer 3 and the adhesive layer 4
- the laminated body of the present invention includes both the cured layer 5 and the layer 6 containing the polyvinyl alcohol resin, as shown in FIG. 2, the light absorption anisotropic layer 3, the cured layer 5, and the layer containing the polyvinyl alcohol resin. It is preferable to have 6 and the adhesive layer 4 in this order.
- the laminate of the present invention preferably further has a surface film 7, as shown in FIG. At this time, it is preferable that the surface film 7 and the adhesive layer 4 are in contact with each other, that is, the surface film 7 and the other layers are bonded together by the adhesive layer 4.
- the laminate of the present invention may be used in a state where the support 1 shown in FIG. 2 is peeled off and the support 1 is not provided as shown in FIG. Further, the laminate of the present invention may further have a retardation film 8 as shown in FIG. 3, and in that case, the retardation film 8 is preferably arranged on the alignment layer 2 side.
- the pressure-sensitive adhesive layer used in the present invention is not particularly limited as to the material used as long as it has a thickness of 5 ⁇ m to 50 ⁇ m, and various known materials can be used.
- the storage elastic modulus of the pressure-sensitive adhesive layer used in the present invention is preferably 10 kPa to 20 MPa, more preferably 10 kPa to 2 MPa, from the viewpoint of making it easier to control the releasability of the support.
- the storage elastic modulus means a value measured at a frequency of 1 Hz and 25 ° C. using a dynamic viscoelasticity measuring device (DVA-200) manufactured by IT Measurement and Control Co., Ltd.
- DVA-200 dynamic viscoelasticity measuring device manufactured by IT Measurement and Control Co., Ltd.
- the pressure-sensitive adhesive layer used in the present invention has a thickness of 5 ⁇ m to 50 ⁇ m, preferably more than 10 ⁇ m and 50 ⁇ m or less. When the content is in the above range, the peelability can be adjusted more easily.
- ⁇ Material used for adhesive layer examples of the material contained in the adhesive layer used in the present invention include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl Examples thereof include a pyrrolidone-based pressure-sensitive adhesive, a polyacrylamide-based pressure-sensitive adhesive, and a cellulose-based pressure-sensitive adhesive. Of these, acrylic adhesives (pressure-sensitive adhesives) are preferable from the viewpoints of transparency, weather resistance, heat resistance, and the like.
- An acrylic polymer such as a copolymer with a (meth) acrylic monomer having a functional group such as acrylate is preferable.
- An adhesive containing such an acrylic polymer has excellent adhesiveness, and even when it is peeled off after being attached to another member, it is relatively easy to cause no adhesive residue on the display device. It is preferable because it can be peeled off.
- the glass transition temperature of such an acrylic polymer is preferably 25 ° C or lower, more preferably 0 ° C or lower.
- the weight average molecular weight of such an acrylic polymer is preferably 100,000 or more.
- the support used in the present invention is not particularly limited, and various known supports can be used.
- the support is preferably a peelable support.
- Examples of the material constituting the support used in the present invention include cellulose resins, acrylic resins, methacrylic resins, polycarbonate resins, polystyrene resins, polyolefin resins, cyclic polyolefin resins, glutaric anhydride resins.
- Examples thereof include resins, glutarimide-based resins, cellulose-based resins, polyester-based resins, and mixed resins of plural kinds of resins selected from these, and among them, cellulose-based resins or polyester-based resins are preferable.
- the thickness of the support is preferably 10 to 200 ⁇ m, more preferably 50 to 200 ⁇ m, and further preferably 100 to 200 ⁇ m from the viewpoint of facilitating the adjustment of the peelability.
- the peelability can be adjusted more easily.
- the adhesiveness of the support / alignment layer can be reduced, so that the releasability can be adjusted more easily.
- the alignment layer used in the present invention is a photo-alignment layer formed using a composition for forming an alignment layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.
- the thickness of the alignment layer used in the present invention is preferably 0.1 ⁇ m to 2 ⁇ m, more preferably more than 0.5 ⁇ m and 2 ⁇ m or less.
- the photo-alignment layer used in the present invention is an alignment layer formation containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond (hereinafter, abbreviated as “polymerizable group” in this paragraph).
- a photo-alignment layer formed by using the composition for use, and among them, a photo-alignment layer formed by using a photo-alignment copolymer described below as a cinnamoyl compound is more preferable.
- a polymerizable group of the same kind as that contained in the composition of the light absorption anisotropic layer is also contained in the composition of the photo-alignment layer so that the layers are chemically bonded to each other. It is advantageous to realize a laminate in which the interlayer adhesion between the photo-alignment layer / the light-absorption anisotropic layer is increased and the support is easily peeled off, which is the subject of the present invention.
- the photo-alignable copolymer used in the present invention comprises a repeating unit A containing a photo-alignable group represented by the following formula (A) and a repeating unit B containing a cross-linkable group represented by the following formula (B). It is a photo-alignable copolymer having and.
- R 1 represents a hydrogen atom or a methyl group.
- L 1 represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and a part of carbon atoms constituting the cycloalkane ring is substituted with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur. It may have been done.
- R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent, and two adjacent groups of R 2 , R 3 , R 4 , R 5 and R 6 May combine with each other to form a ring.
- R 7 represents a hydrogen atom or a methyl group
- L 2 represents a divalent linking group
- X represents a crosslinkable group represented by the following formula (X4).
- * represents a bonding position with L 2 in the above formula (B)
- S represents a functional group having an ethylenically unsaturated double bond.
- a photoalignable copolymer having a repeating unit A containing a photoalignable group represented by the above formula (A) and a repeating unit B containing a crosslinkable group represented by the above formula (B).
- the use of the combination improves the solvent resistance and liquid crystal alignment of the obtained photo-alignment film.
- the divalent linking group represented by L 1 in the above formula (A) contains a nitrogen atom and a cycloalkane ring, hydrogen bonding and molecular rigidity are enhanced, and thus molecular motion is suppressed. As a result, it is considered that the solvent resistance was improved.
- the divalent linking group represented by L 1 in the above formula (A) contains a nitrogen atom and a cycloalkane ring
- the glass transition temperature of the copolymer is increased and the resulting photo-alignment is achieved. It is considered that, as a result of the improvement in the temporal stability of the film, the liquid crystal alignment was improved regardless of the timing of forming the optically anisotropic layer.
- the divalent linking group containing a nitrogen atom and a cycloalkane ring represented by L 1 in the above formula (A) will be described.
- a part of the carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur.
- the nitrogen atom may not be present separately from the cycloalkane ring.
- the cycloalkane ring contained in the divalent linking group represented by L 1 in the above formula (A) is preferably a cycloalkane ring having 6 or more carbon atoms, and specific examples thereof include a cyclohexane ring and cyclopeptane. Examples thereof include a ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring.
- L 1 in the above formula (A) is a divalent linking group represented by any one of the following formulas (1) to (10) for the reason that the liquid crystal orientation is better. It is preferable.
- * 1 represents a bonding position with a carbon atom constituting the main chain in the above formula (A)
- * 2 represents a carbonyl group in the above formula (A). It represents the bond position with the constituent carbon atom.
- divalent linking group represented by any of the above formulas (1) to (10) the solubility in the solvent used when forming the photo-alignment film and the solvent resistance of the obtained photo-alignment film From the reason of good balance, a divalent linking group represented by any of the above formulas (2), (3), (7) and (8) is preferable.
- L 1 in the above formula (A) may be a divalent linking group other than the above-mentioned “divalent linking group containing a nitrogen atom and a cycloalkane ring”.
- a photo-alignment group is likely to interact with a liquid crystal compound, and even if it has a substituent, the liquid crystal alignment property of the adjacent liquid crystal layer is improved.
- R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) may be hydrogen atoms instead of substituents.
- * represents a bonding position with the benzene ring in the formula (A)
- R 9 represents a monovalent organic group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
- the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, methyl group, ethyl group. Group, n-propyl group and the like.
- the branched alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include an isopropyl group and a tert-butyl group.
- the cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.
- the linear halogenated alkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group and a perfluoropropyl group. , A perfluorobutyl group, and the like, among which a trifluoromethyl group is preferable.
- an alkoxy group having 1 to 20 carbon atoms an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 6 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 14 carbon atoms is further preferable.
- Preferable examples thereof include a group, and among them, an n-hexyloxy group, an n-octyloxy group, an n-decyloxy group, an n-dodecyloxy group and an n-tetradecyloxy group are more preferable.
- the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group and a naphthyl group. Among them, a phenyl group is preferable. preferable.
- the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenyloxy group and a 2-naphthyloxy group. Is preferred.
- amino group examples include a primary amino group (—NH 2 ); a secondary amino group such as a methylamino group; a dimethylamino group, a diethylamino group, a dibenzylamino group, a nitrogen-containing heterocyclic compound (eg, pyrrolidine , Piperidine, piperazine, etc.) and tertiary amino groups such as groups having a nitrogen atom as a bond.
- a primary amino group —NH 2
- secondary amino group such as a methylamino group
- a dimethylamino group a diethylamino group
- a dibenzylamino group examples include a nitrogen-containing heterocyclic compound (eg, pyrrolidine , Piperidine, piperazine, etc.) and tertiary amino groups such as groups having a nitrogen atom as a bond.
- examples of the monovalent organic group represented by R 9 in the above formula (11) include a linear or cyclic alkyl group having 1 to 20 carbon atoms.
- the linear alkyl group an alkyl group having 1 to 6 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. Among them, a methyl group or an ethyl group is preferable. preferable.
- cyclic alkyl group an alkyl group having 3 to 6 carbon atoms is preferable, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and among them, a cyclohexyl group is preferable.
- the monovalent organic group represented by R 9 in the above formula (11) may be a combination of a plurality of the above linear alkyl groups and cyclic alkyl groups directly or through a single bond. Good.
- R 2 , R 3 , R 4 , R 5 in the above formula (A) and the photo-alignment group are more likely to interact with the liquid crystal compound, resulting in better liquid crystal alignment.
- at least R 4 of R 6 represents the above-mentioned substituent, and further the linearity of the obtained photo-alignable copolymer is improved, and the photo-alignable copolymer easily interacts with the liquid crystalline compound, resulting in liquid crystal alignment.
- all of R 2 , R 3 , R 5 and R 6 represent a hydrogen atom for the reason that the property is further improved.
- R 4 in the above formula (A) is preferably an electron-donating substituent because the reaction efficiency is improved when the resulting photo-alignment film is irradiated with light.
- the electron-donating substituent refers to a substituent having a Hammett value (Hammett substituent constant ⁇ p) of 0 or less.
- an alkyl group examples thereof include halogenated alkyl groups and alkoxy groups.
- an alkoxy group is preferable, and an alkoxy group having 6 to 16 carbon atoms is more preferable, and an alkoxy group having 7 to 10 carbon atoms is preferable, for the reason that the liquid crystal alignment property is more improved. Is more preferable.
- the photo-alignment group is more likely to interact with the liquid crystal compound, and the liquid crystal alignment property is more improved.
- a chain, branched or cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C ( O)-), and It is preferably a divalent linking group in which at least two groups selected from the group consisting of an imino group (—NH—) which may have a substituent are combined.
- examples of the substituent that the alkylene group, the arylene group and the imino group may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a carboxy group and an alkoxycarbonyl group. And hydroxyl groups.
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
- alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group. Is particularly preferable.
- an alkyl group having 1 to 8 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group
- N-butyl group isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.
- an alkyl group having 1 to 4 carbon atoms
- an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable. It is more preferably an alkoxy group of the formula 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
- the aryl group include an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group and a naphthyl group, and among them, a phenyl group is preferable.
- Examples of the aryloxy group include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, thiophen-3-yloxy and the like.
- Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.
- linear alkylene group having 1 to 18 carbon atoms specific examples include methylene group, ethylene group, propylene group, butylene group, pentylene group, Examples include a hexylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.
- branched alkylene group examples include dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, 2-ethyl-2-methylpropylene group and the like.
- cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group and a norbornane-diyl group.
- Exo-tetrahydrodicyclopentadiene-diyl group and the like among which a cyclohexylene group is preferable.
- arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group and a 2,2′-methylenebisphenyl group.
- the phenylene group is preferable. .
- X (crosslinkable group) in the above formula (B) is a crosslinkable group represented by the following formula (X4) among the crosslinkable groups represented by the following formulas (X1) to (X4).
- * represents a bonding position with L 2 in the formula (B)
- R 8 represents any one of a hydrogen atom, a methyl group and an ethyl group.
- S represents a functional group having an ethylenically unsaturated double bond.
- specific examples of the functional group having an ethylenically unsaturated double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group. Is preferred.
- the repeating unit B is used for the reason that the strength of the optical layered body of the present invention described later becomes high and the handling property when forming other layers using the optical layered body of the present invention described later becomes good.
- X in the above formula (B) is a crosslinkable group represented by any of the above formulas (X1) to (X3) (hereinafter also abbreviated as “repeating unit B1”), and the above formula.
- X in (B) contains a repeating unit which is a crosslinkable group represented by the above formula (X4) (hereinafter, also abbreviated as “repeating unit B2”).
- repeating unit A containing a photoalignable group represented by the above formula (A) include repeating units A-1 to A-44 shown below.
- Me represents a methyl group
- Et represents an ethyl group.
- the “1,4-cyclohexyl group” contained in the divalent linking group of the repeating units A-1 to A-10 may be either cis or trans isomer, The trans form is preferred.
- repeating unit B (repeating unit B1) containing a crosslinkable group represented by the above formula (B) include repeating units B-1 to B-17 shown below.
- repeating unit B (repeating unit B2) containing a crosslinkable group represented by the above formula (B) include repeating units B-18 to B-47 shown below.
- the content a of the repeating unit A described above and the content b of the repeating unit B described above satisfy the following formula (12) in mass ratio. It is more preferable that the following expression (13) is satisfied, it is further preferable that the following expression (14) is satisfied, and it is particularly preferable that the following expression (15) is satisfied. 0.03 ⁇ a / (a + b) ⁇ 0.5 (12) 0.03 ⁇ a / (a + b) ⁇ 0.3 (13) 0.03 ⁇ a / (a + b) ⁇ 0.2 (14) 0.05 ⁇ a / (a + b) ⁇ 0.2 (15)
- the photo-alignable copolymer used in the present invention has the above-mentioned repeating unit B2 together with the above-mentioned repeating unit B1, it has an optical anisotropy containing a photo-alignment film while maintaining good liquid crystal alignment and adhesion.
- the content a of the repeating unit A described above, the content b1 of the repeating unit B1 described above, and the content b2 of the repeating unit B2 described above are as follows in terms of mass ratio. It is preferable that the expression (16) is satisfied, and it is more preferable that the following expression (17) is satisfied. 0.05 ⁇ b2 / (a + b1 + b2) ⁇ 0.7 (16) 0.10 ⁇ b2 / (a + b1 + b2) ⁇ 0.5 (17)
- the photoalignable copolymer used in the present invention may have another repeating unit other than the above-mentioned repeating unit A and repeating unit B as long as the effects of the present invention are not impaired.
- Examples of such other repeating unit-forming monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, Examples thereof include vinyl compounds.
- the method for synthesizing the photoalignable copolymer used in the present invention is not particularly limited, and examples thereof include the monomer forming the repeating unit A described above, the monomer forming the repeating unit B described above, and any other repeating unit. It can be synthesized by mixing the monomers that form the compound and polymerizing in an organic solvent using a radical polymerization initiator.
- the weight average molecular weight (Mw) of the photo-alignable copolymer used in the present invention is preferably 10,000 to 500,000, more preferably 30,000 to 300,000 because the liquid crystal alignment is further improved.
- the weight average molecular weight and the number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method under the following conditions.
- the light absorption anisotropic layer used in the present invention is a layer having a different degree of light absorption depending on the direction, and usually has an absorption axis and a polarization axis (transmission axis).
- the thickness of the light absorption anisotropic layer used in the present invention is preferably 0.1 ⁇ m to 3 ⁇ m, more preferably 0.1 ⁇ m to 2 ⁇ m.
- the light absorption anisotropic layer used in the present invention preferably contains a dichroic substance. Further, the light absorption anisotropic layer used in the present invention preferably contains a liquid crystal compound together with the dichroic substance. The light absorption anisotropic layer used in the present invention preferably contains a dichroic azo compound.
- the dichroic substance used in the present invention is not particularly limited, and a visible light absorbing substance (dichroic dye, dichroic azo compound), a luminescent substance (fluorescent substance, phosphorescent substance), an ultraviolet absorbing substance, an infrared absorbing substance.
- a visible light absorbing substance dichroic dye, dichroic azo compound
- a luminescent substance fluorescent substance, phosphorescent substance
- an ultraviolet absorbing substance an infrared absorbing substance.
- Non-linear optical substances, carbon nanotubes, inorganic substances (for example, quantum rods), and the like, and conventionally known dichroic substances (dichroic dyes) can be used.
- a dichroic substance having liquid crystallinity is also preferable.
- paragraph, paragraphs [0014] to [0033] of WO 2017/154835 , [0014] to [0033] of WO 2017/154695 paragraph [0013] of WO 2017/195833 include to [0037] those described in such paragraphs.
- two or more dichroic substances may be used in combination, and for example, from the viewpoint of bringing the polarizer close to black, at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 370 to 550 nm. It is preferable to use the substance in combination with at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 500 to 700 nm.
- the dichroic material may have a crosslinkable group.
- the crosslinkable group include a (meth) acryloyl group, an epoxy group, an oxetanyl group, and a styryl group. Among them, a (meth) acryloyl group is preferable.
- the above-mentioned dichroic substance is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and further preferably 10 to 30% by mass based on the solid content of the light absorption anisotropic layer.
- liquid crystal compound used in the present invention both a low molecular weight liquid crystal compound and a high molecular weight liquid crystal compound can be used.
- the “low molecular weight liquid crystal compound” refers to a liquid crystal compound having no repeating unit in its chemical structure.
- polymer liquid crystal compound refers to a liquid crystal compound having a repeating unit in its chemical structure.
- Examples of the low molecular weight liquid crystal compound include liquid crystal compounds described in JP 2013-228706 A.
- polymer liquid crystalline compound examples include the thermotropic liquid crystalline polymer described in JP 2011-237513 A. Further, the polymer liquid crystalline compound may have a crosslinkable group (eg, acryloyl group and methacryloyl group) at the terminal.
- crosslinkable group eg, acryloyl group and methacryloyl group
- the liquid crystal compound used in the present invention is preferably a liquid crystal compound having a polymerizable group (polymerizable liquid crystal compound).
- the polymerizable group include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, a (meth) acryloyl group is preferable.
- the liquid crystal compounds may be used alone or in combination of two or more. Further, in the present invention, it is preferable to contain a high molecular weight liquid crystalline compound, and it is more preferable to use a low molecular weight liquid crystalline compound together with the high molecular weight liquid crystalline compound.
- the content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 33 to 1000 parts by mass, and further preferably 50 to 500 parts by mass, relative to 100 parts by mass of the dichroic substance content.
- the degree of alignment of the polarizer is further improved.
- the optional hardened layer used in the present invention is preferably a hardened layer having a thickness of 100 nm or less.
- the hardened layer various known ones can be used. Examples thereof include a layer containing a liquid crystal compound and a layer obtained by curing a composition containing a polyfunctional monomer. It is preferable to have a refractive index capable of performing index matching with the light absorption anisotropic layer.
- the layer containing a polyvinyl alcohol resin (PVA layer) used in the present invention is preferably a layer containing a polyvinyl alcohol resin having a thickness of 2 ⁇ m or less.
- the optional surface film used in the present invention is usually preferably arranged on the outermost side in the obtained optical laminate.
- the surface film is not particularly limited and various known ones can be used.
- an embodiment in which the surface film has a hard coat layer and a substrate can be mentioned.
- Examples of the material forming the surface film include (meth) acrylic resins, polycarbonate resins, polystyrene resins, polyolefin resins, cyclic polyolefin resins, glutaric anhydride resins, glutarimide resins, and cellulose resins. , Polyester-based resins, polyimide-based resins, and mixed resins of plural kinds of resins selected from these, among them, cyclic polyolefin-based resins, (meth) acrylic-based resins, polyimide-based resins, or polyester-based resins Is preferred. In addition, a polyimide resin is preferable from the viewpoint of excellent flexibility.
- the surface film may contain an ultraviolet absorber.
- Examples of the (meth) acrylic resin include, in addition to methacrylic resin and acrylic resin, a (meth) acrylic polymer having a ring structure in its main chain, that is, a polymer having a lactone ring and a succinic anhydride ring. And a maleic anhydride-based polymer having, a polymer having a glutaric anhydride ring, a glutarimide ring-containing polymer, and the like.
- the hard coat layer is a layer for imparting hardness or scratch resistance to the laminate.
- the hard coat layer can be formed, for example, by applying the composition for forming a hard coat layer on a substrate and curing the composition. Further, another functional layer may be laminated on the hard coat layer for the purpose of adding another function. Further, by adding a filler or an additive to the hard coat layer, it is possible to impart mechanical, electrical or optical physical performance, or chemical performance such as water repellency or oil repellency to the hard coat layer itself. .
- the hard coat layer preferably has excellent scratch resistance. Specifically, it is preferable to achieve 3H or more when a pencil hardness test, which is an index of scratch resistance, is performed.
- the thickness of the hard coat layer is preferably 0.1 to 6 ⁇ m, more preferably 3 to 6 ⁇ m.
- the hard coat layer is preferably formed by curing the curable composition.
- the curable composition is preferably prepared as a liquid coating composition.
- One example of the curable composition includes a monomer for forming a matrix-forming binder, an oligomer, or a polymer, and an organic solvent.
- the surface film is not limited to an embodiment having a base material and a hard coat layer, and may be, for example, only the base material or only the hard coat layer.
- the in-plane retardation value of the retardation film is not particularly limited, and the retardation film may be a ⁇ / 4 plate or a ⁇ / 2 plate. Further, it may be a retardation film composed of a plurality of layers.
- the “ ⁇ / 4 plate” is a plate having a ⁇ / 4 function, and specifically, converts linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). It is a plate that has a function to do.
- the ⁇ / 4 plate has a single layer structure, specifically, a stretched polymer film, a retardation film in which an optically anisotropic layer having a ⁇ / 4 function is provided on a support, and the like can be mentioned.
- a broadband ⁇ / 4 plate formed by laminating a ⁇ / 4 plate and a ⁇ / 2 plate can be mentioned.
- the material constituting the retardation film is not particularly limited, and examples thereof include various polymer films and layers containing various liquid crystal compounds.
- An image display device of the present invention includes the above-mentioned laminated body and an image display element.
- the image display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
- EL organic electroluminescence
- a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable.
- the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as an image display element and an organic EL display device using an organic EL display panel as a display element, and is preferably an organic EL display device. Is more preferable.
- the liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to these.
- VA Vertical Alignment
- OCB Optically Compensated Bend
- IPS In-Plane-Switching
- TN Transmission Nematic
- rod-shaped liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and further twisted and aligned at 60 to 120 °.
- the TN mode liquid crystal cell is most often used as a color TFT (Thin Film Transistor) liquid crystal display device, and is described in many documents.
- VA mode liquid crystal cell rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied.
- the VA mode liquid crystal cell includes (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and are aligned substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. HEI 2-200868). 176625), (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceedings) 28 (1997) 845) in which the VA mode is multi-domain (MVA mode) for widening the viewing angle.
- a liquid crystal cell of a mode in which rod-like liquid crystal molecules are substantially vertically aligned when no voltage is applied and twisted in multiple domains when a voltage is applied (Proceedings 58-59 of the Japan Liquid Crystal Conference). (1998)) and (4) SURVIVAL mode liquid crystal cell (announced at LCD International 98).
- any of a PVA (Patterned Vertical Alignment) type, a photo alignment type (Optical Alignment), and a PSA (Polymer-Sustained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-A-2008-538819.
- IPS mode liquid crystal cell rod-shaped liquid crystalline molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane when an electric field parallel to the substrate surface is applied.
- black display occurs when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
- a method of reducing leakage light at the time of black display in an oblique direction and improving a viewing angle by using an optical compensation sheet is disclosed in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522.
- Organic EL display device As an organic EL display device which is an example of the image display device of the present invention, for example, a mode in which the laminate of the present invention described above and the organic EL display panel are provided in this order from the viewing side is preferable. More preferably, the laminated body of the present invention having a ⁇ / 4 plate and the organic EL display panel are provided in this order from the viewing side. In this case, the laminate is arranged in the order of the surface film, the pressure-sensitive adhesive layer, the light absorption anisotropic layer, the alignment layer, and the retardation film from the viewing side, if necessary.
- the organic EL display panel is a display panel configured by using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode).
- the structure of the organic EL display panel is not particularly limited, and a known structure is adopted.
- Example 1 ⁇ Formation of photo-alignment layer PA1>
- a TAC (triacetyl cellulose) film (TJ40UL, thickness 40 ⁇ m, manufactured by FUJIFILM Corporation) was used.
- the composition PA1 for forming an alignment layer described below was continuously applied onto the support with a wire bar.
- the support on which the coating film is formed is dried with warm air of 140 ° C. for 120 seconds, and then the coating film is irradiated with polarized ultraviolet rays (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to obtain a photo-alignment layer.
- PA1 was formed to obtain a TAC film with a photo-alignment layer.
- the film thickness of the photo-alignment layer PA1 was 1.0 ⁇ m.
- a composition P1 for forming a light-absorption anisotropic layer having the following composition was continuously applied onto the obtained photo-alignment layer PA1 with a wire bar to form a coating layer P1.
- the coating layer P1 was heated at 140 ° C. for 90 seconds, and the coating layer P1 was cooled to room temperature (23 ° C.). Then, it heated at 80 degreeC for 60 second, and cooled again to room temperature.
- the light absorption anisotropic layer P1 was formed on the photo-alignment layer PA1 by performing irradiation for 60 seconds using a high pressure mercury lamp under irradiation conditions of an illuminance of 28 mW / cm 2 .
- the film thickness of the light absorption anisotropic layer P1 was 0.4 ⁇ m.
- composition P1 for forming light absorption anisotropic layer ⁇ 0.25 parts by mass of the following azo dye Y-1 0.27 parts by mass of the following azo dye M-1 0.65 parts by mass of the following azo dye C-1 3.59 parts by mass of the following polymeric liquid crystalline compound P-1 Parts-Liquid crystal compound L-1 0.12 parts by mass-Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.200 parts by mass-Interface modifier F-1 0.026 parts by mass-Cyclopentanone 47.50 Mass part / tetrahydrofuran 47.50 mass part ⁇
- the composition L1 for forming a cured layer having the following composition was continuously applied with a wire bar to form a composition layer L1.
- the composition layer L1 was dried at room temperature, and then irradiated with a high pressure mercury lamp under irradiation conditions of an illuminance of 28 mW / cm 2 for 10 seconds to form a cured layer L1 on the light absorption anisotropic layer P1.
- the film thickness of the cured layer L1 was 30 nm.
- composition L1 ⁇ -Mixture of rod-like liquid crystalline compound L-2 2.43 parts by mass-modified trimethylolpropane triacrylate 0.98 parts by mass-photopolymerization initiator I-1 0.20 parts by mass-interface improver F- 1 0.14 parts by mass ⁇ 1,4-phenylenediboronic acid (Tokyo Kasei) 0.10 parts by mass ⁇ methyl ethyl ketone 371 parts by mass ⁇ ⁇
- a coating solution B1 for forming a polyvinyl alcohol (PVA) layer having the following composition was continuously coated on the cured layer L1 with a wire bar. Then, the PVA layer having a thickness of 1.0 ⁇ m was formed on the hardened layer L1 by drying with warm air of 100 ° C. for 2 minutes.
- ⁇ Coating liquid B1 for PVA layer formation ⁇ ⁇
- the following modified polyvinyl alcohol 3.80 parts by mass ⁇ Initiator Irg2959 0.20 parts by mass ⁇ Water 70 parts by mass ⁇ Methanol 30 parts by mass ⁇ ⁇
- the prepared pressure-sensitive adhesive composition N1 was applied onto a silicone resin-coated PET film (hereinafter, also referred to as “release film”), and the solvent was removed by drying at 90 ° C., and the thickness was 20 ⁇ m.
- An adhesive sheet N1 having an adhesive layer N1 was produced.
- the storage elastic modulus of the adhesive layer N1 was 0.3 MPa.
- Example 2 A laminate of Example 2 was obtained in the same manner as in Example 1 except that the support was changed to PET (thickness 40 ⁇ m) in the formation of the light absorption anisotropic layer of Example 1.
- Example 3 was repeated in the same manner as in Example 1 except that the support was changed to the cellulose acylate film TJ100UL (thickness: 100 ⁇ m, manufactured by Fujifilm Corporation) in the formation of the light-absorption anisotropic layer of Example 1. A laminated body of was obtained.
- Examples 4 to 7 In the formation of the light-absorption anisotropic layer of Example 1, the composition for forming the light-absorption anisotropic layer and the thickness of the photo-alignment layer were respectively changed as shown in Table 2 below, and as in Example 1. By the same method, laminates of Examples 4 to 7 were obtained. In addition, in Table 2 below, the details of the compositions P2 and P3 for forming the light absorption anisotropic layer are as follows.
- composition P2 for forming light absorption anisotropic layer ⁇ 0.25 parts by mass of the azo dye Y-1. 0.27 parts by mass of the azo dye M-1. 0.65 parts by mass of the following azo dye C-2. 3.71 parts by mass of the following polymeric liquid crystalline compound P-2.
- Parts-Polymerization initiator IRGACUREOXE-03 manufactured by BASF 0.151 parts by mass-The above interface improver F-1 0.026 parts by mass-Cyclopentanone 47.50 parts by mass-Tetrahydrofuran 47.50 parts by mass --- ⁇
- Parts-Polymerization initiator IRGACUREOXE-03 manufactured by BASF 0.151 parts by mass-The interface improver F-1 0.026 parts by mass-Cyclopentanone 47.50 parts by mass-Tetrahydrofuran 47.50 parts by mass ---- ⁇
- Example 8 ⁇ Formation of the light absorption anisotropic layer P4> A photo-alignment layer PA1 was formed in the same manner as in Example 1 to obtain a TAC film with a photo-alignment layer.
- the composition P4 for forming a light-absorption anisotropic layer prepared below was continuously applied onto the obtained photo-alignment layer PA1 with a wire bar to form a coating layer P4.
- the coating layer P4 was heated at 120 ° C. for 60 seconds, and the coating layer P4 was cooled to room temperature (23 ° C.).
- the light absorption anisotropic layer P4 was formed on the photo-alignment layer PA1 by performing irradiation for 60 seconds using a high-pressure mercury lamp under irradiation conditions of an illuminance of 28 mW / cm 2 .
- the film thickness of the light absorption anisotropic layer P4 was 1.7 ⁇ m.
- composition P4 for forming a light-absorption anisotropic layer having the following composition was prepared, heated and dissolved at 50 ° C. for 3 hours with stirring, and filtered through a 0.45 ⁇ m filter.
- ⁇ Composition P4 for forming light absorption anisotropic layer ⁇ ⁇ 2.7 parts by mass of the following azo dye Y-3 ⁇ 2.7 parts by mass of the following azo dye M-3 ⁇ 2.7 parts by mass of the following azo dye C-4 ⁇ 75.5 parts by mass of the following liquid crystal compound P-3 ⁇ polymerization Initiator IRGACURE 819 (manufactured by BASF) 0.8 parts by mass-The above-mentioned interface improver F-1 0.6 parts by mass-Cyclopentanone 274.5 parts by mass-Tetrahydrofuran 640.5 parts by mass ------------ ⁇
- Example 9 to 16 In the formation of the pressure-sensitive adhesive layer of Example 1, among the pressure-sensitive adhesive layers in the above-mentioned pressure-sensitive adhesive sheet N1 and pressure-sensitive adhesive sheets N2 to N6 described below, the pressure-sensitive adhesive layer shown in Table 2 below was used, and the thickness was changed to that shown in Table 2 below. In the same manner as in Example 1, laminates of Examples 9 to 16 were obtained.
- the prepared pressure-sensitive adhesive composition N2 was applied onto a silicone resin-coated PET film (release film), and the solvent was removed by drying at 90 ° C., and ultraviolet rays (UV) were irradiated under the following conditions.
- An adhesive sheet N2 having an adhesive layer N2 having a thickness of 20 ⁇ m was produced.
- the storage elastic modulus of the adhesive layer N2 was 0.6 MPa. (UV irradiation conditions) ⁇ Fusion's electrodeless lamp H bulb ⁇ Illuminance: 600 mW / cm 2 ⁇ Light intensity: 150 mJ / cm 2 The UV illuminance and the light intensity were measured using "UVPF-36" manufactured by Eye Graphics.
- an acrylic polymer was prepared according to the following procedure.
- a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer 70 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of ethyl acrylate, 6 parts by mass of hydroxyethyl methacrylate and 4 parts by mass of acrylic acid were dissolved.
- Polymerization was performed by a polymerization method to obtain an acrylic polymer A1 having an average molecular weight of 300,000.
- pressure-sensitive adhesive sheets N3 to N5 were produced according to the following procedure.
- the prepared pressure-sensitive adhesive composition N6 is applied onto a silicone resin-coated PET film (release film), and the solvent is removed by drying at 90 ° C., and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer N6 of 25 ⁇ m in thickness. N6 was produced.
- the storage elastic modulus of the adhesive layer N6 was 0.1 MPa.
- Example 17 A laminate of Example 17 was obtained in the same manner as in Example 15, except that TJ100UL (thickness 100 ⁇ m, manufactured by Fuji Film Co., Ltd.) was used instead of TJ40UL as the support.
- TJ100UL thickness 100 ⁇ m, manufactured by Fuji Film Co., Ltd.
- Comparative Example 1 A laminate of Comparative Example 1 was obtained in the same manner as in Example 10 except that the thickness of the adhesive layer was changed to the values shown in Table 2 below.
- Comparative Example 2 A laminated body of Comparative Example 2 was obtained in the same manner as in Example 1 except that the composition PA1 for forming an alignment layer was changed to the composition PA2 for forming an alignment layer.
- the thickness between the support and the adhesive layer excluding the thickness of the support and the adhesive layer, is 5 ⁇ m or less, the thickness of the adhesive layer is 5 to 50 ⁇ m, and the alignment layer is It has been found that the support can be easily peeled off in the case of a photo-alignment layer formed using the composition for forming an alignment layer containing a cinnamoyl compound having a functional group having a saturated double bond (Examples 1-17).
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Abstract
Description
例えば、特許文献1には、「液晶硬化膜と、粘接着剤層と、位相差フィルムと、粘接着剤層とをこの順に積層した円偏光板であって、該液晶硬化膜が、重合性液晶化合物が基材面内に対して水平方向に配向した状態で硬化した厚さが3μm以下の膜であって、二色性色素を含む膜である円偏光板。」が開示されている([請求項16])。
そして、特許文献1では、薄型の光学異方性フィルムを与える光学異方性シートを提供することを課題としている([0004])。
特に、偏光子等が薄型化している等の理由により各層が非常に薄い積層体の場合、剥離界面のコントロールは更に難易度が高いことが分かった。例えば、支持体、配向層および光吸収異方性層を有する積層体から、支持体のみを剥離しようとしても、配向層と光吸収異方性層との界面で剥離が起こってしまうことがあった。
すなわち、支持体、配向層、光吸収異方性層および粘着層をこの順に有し、支持体および粘着層を含まない支持体から粘着層までの間の厚みが5μm以下である積層体において、粘着層の厚みを特定の値とすることで、支持体のみを剥離することが容易となる積層体を提供することができることを見出した。
支持体および粘着層を含まない支持体から粘着層までの間の厚みが5μm以下であり、
粘着層の厚みが、5μm~50μmであり、
配向層が、エチレン性不飽和二重結合を有する官能基を有するシンナモイル化合物を含有する配向層形成用組成物を用いて形成した光配向層である、積層体。
[2] 粘着層の貯蔵弾性率が、100kPa~20MPaである、[1]に記載の積層体。
[3] 粘着層の貯蔵弾性率が、100kPa~2MPaである、[2]に記載の積層体。
[4] 粘着層の厚みが、10μm超50μm以下である、[1]~[3]のいずれかに記載の積層体。
[5] 光吸収異方性層が、二色性物質と液晶性化合物とを含む、[1]~[4]のいずれかに記載の積層体。
[6] 光吸収異方性層が、二色性アゾ化合物を含む、[1]~[5]のいずれかに記載の積層体。
[7] 光吸収異方性層の厚みが、0.1μm~3μmである、[1]~[6]のいずれかに記載の積層体。
[8] 配向層の厚みが、0.1μm~2μmである、[1]~[7]のいずれかに記載の積層体。
[9] 配向層の厚みが、0.5μm超2μm以下である、[8]に記載の積層体。
[10] シンナモイル化合物が、後述する式(A)で表される光配向性基を含む繰り返し単位Aと、後述する式(B)で表される架橋性基を含む繰り返し単位Bとを有する、光配向性共重合体である、[1]~[9]のいずれかに記載の積層体。
[11] 後述する式(A)中のL1が、後述する式(1)~(10)のいずれかで表される2価の連結基である、[10]に記載の積層体。
[12] 液晶性化合物が、重合性液晶化合物である、[5]に記載の積層体。
[13] 液晶性化合物が、高分子液晶性化合物である、[5]に記載の積層体。
[14] 光吸収異方性層が、更に低分子液晶性化合物を含む、[13]に記載の積層体。
[15] 光吸収異方性層と粘着層との間に、更に厚さ100nm以下の硬化層を有する、[1]~[14]のいずれかに記載の積層体。
[16] 硬化層が液晶性化合物を含む、[15]に記載の積層体。
[17] 硬化層が多官能モノマーを含む組成物を硬化させた層である、[15]に記載の積層体。
[18] 光吸収異方性層と粘着層との間に、更に厚さ2μm以下のポリビニルアルコール樹脂を含む層を有する、[1]~[17]のいずれかに記載の積層体。
[19] 支持体と配向層とが接している、[1]~[18]のいずれかに記載の積層体。
[20] 配向層と光吸収異方性層とが接している、[1]~[19]のいずれかに記載の積層体。
[21] [1]~[20]のいずれかに記載の積層体と、表面フィルムとを有し、粘着層と表面フィルムとが接している、積層体。
[22] 支持体が剥離された、[21]に記載の積層体。
[23] 更に位相差フィルムを有し、位相差フィルムが配向層側に配置された、[22]に記載の積層体。
[24] [1]~[23]のいずれかに記載の積層体と、画像表示素子とを有する、画像表示装置。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、本明細書において、平行、直交とは厳密な意味での平行、直交を意味するのではなく、平行または直交から±5°の範囲を意味する。
また、本明細書において、「(メタ)アクリレート」は、「アクリレート」または「メタクリレート」を表す表記であり、「(メタ)アクリル」は、「アクリル」または「メタクリル」を表す表記であり、「(メタ)アクリロイル」は、「アクリロイル」または「メタクリロイル」を表す表記である。
また、本明細書において、液晶性組成物、液晶性化合物とは、硬化等により、もはや液晶性を示さなくなったものも概念として含まれる。
本発明の積層体は、支持体、配向層、光吸収異方性層、および、粘着層をこの順に有する積層体である。
また、本発明の積層体は、支持体および粘着層を含まない支持体から粘着層までの間の厚みが5μm以下であり、かつ、粘着層の厚みが、5μm~50μmである。
更に、本発明の積層体は、配向層が、エチレン性不飽和二重結合を有する官能基を有するシンナモイル化合物を含有する配向層形成用組成物を用いて形成した光配向層である。
次に、本発明の積層体の全体の構成を図1~図3を用いて説明した後に、各構成について詳述する。
また、積層体10は、支持体1および粘着層4を含まない支持体1から粘着層4までの間の厚み、すなわち支持体1の配向層2側の表面から粘着層4の光吸収異方性層3側の表面までの距離が5μm以下であり、1μm~4μmであることが好ましい。
また、積層体10は、粘着層4の厚みは5μm~50μmである。
また、本発明の積層体は、図1に示すように、配向層2と光吸収異方性層3とが接していることが好ましい。
本発明の積層体は、硬化層5とポリビニルアルコール樹脂を含む層6とを共に含む場合は、図2に示すように、光吸収異方性層3、硬化層5、ポリビニルアルコール樹脂を含む層6および粘着層4をこの順に有することが好ましい。
また、本発明の積層体は、図3に示すように、更に位相差フィルム8を有していてもよく、その場合、位相差フィルム8は配向層2側に配置されるのが好ましい。
本発明に用いられる粘着層は、厚みが5μm~50μmであれば、用いる素材としては特に限定はなく、各種公知の素材を用いることができる。
本発明において貯蔵弾性率は、アイティー計測制御株式会社製の動的粘弾性測定装置(DVA-200)を用いて、周波数1Hz、25℃にて測定した値をいう。
上記範囲とすることで剥離性の調整がより容易となる。
本発明に用いられる粘着層に含まれる素材としては、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、および、セルロース系粘着剤等が挙げられる。
これらのうち、透明性、耐候性、耐熱性などの観点から、アクリル系粘着剤(感圧粘着剤)であるのが好ましい。
このようなアクリル系ポリマーを含む粘着剤は、粘着性に優れており、また、他部材に貼合した後に、剥離する際も、表示装置に糊残り等を生じさせることなく、比較的容易に剥離することが可能であるため好ましい。
また、このようなアクリル系ポリマーのガラス転移温度は、25℃以下が好ましく、0℃以下がより好ましい。
また、このようなアクリル系ポリマーの重量平均分子量は、10万以上であることが好ましい。
本発明に用いられる支持体は、特に限定されず、各種公知のものが使用できる。支持体としては剥離可能な支持体であることが好ましい。
本発明に用いられる配向層は、エチレン性不飽和二重結合を有する官能基を有するシンナモイル化合物を含有する配向層形成用組成物を用いて形成した光配向層である。
本発明に用いられる光配向性共重合体は、下記式(A)で表される光配向性基を含む繰り返し単位Aと、下記式(B)で表される架橋性基を含む繰り返し単位Bとを有する、光配向性の共重合体である。
上記式(B)中、R7は、水素原子またはメチル基を表し、L2は、2価の連結基を表し、Xは、下記式(X4)で表される架橋性基を表す。
これは、詳細には明らかではないが、本発明者らは以下のように推測している。
すなわち、上記式(A)中のL1で表される2価の連結基が、窒素原子とシクロアルカン環とを含むことにより、水素結合性および分子剛直性が高まることで分子運動が抑制され、その結果、耐溶剤性が向上したと考えられる。
同様に、上記式(A)中のL1で表される2価の連結基が、窒素原子とシクロアルカン環とを含むことにより、共重合体のガラス転移温度が上昇し、得られる光配向膜の経時安定性が向上した結果、光学異方性層を形成するタイミングに寄らず、液晶配向性が良好になったと考えられる。
このような2価の連結基としては、光配向性基が液晶性化合物と相互作用しやすくなり、隣接する液晶層の液晶配向性がより良好となる理由から、置換基を有していてもよい炭素数1~18の直鎖状、分岐状または環状のアルキレン基、置換基を有していてもよい炭素数6~12のアリーレン基、エーテル基(-O-)、カルボニル基(-C(=O)-)、および、置換基を有していてもよいイミノ基(-NH-)からなる群から選択される少なくとも2以上の基を組み合わせた2価の連結基であることが好ましい。
分岐状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、イソプロピル基、tert-ブチル基などが挙げられる。
環状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられる。
直鎖状のアルキル基としては、炭素数1~6のアルキル基が好ましく、具体的には、例えば、メチル基、エチル基、n-プロピル基などが挙げられ、中でも、メチル基またはエチル基が好ましい。
環状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられ、中でも、シクロヘキシル基が好ましい。
なお、上記式(11)中のR9が表す1価の有機基としては、上述した直鎖状のアルキル基および環状のアルキル基を直接または単結合を介して複数組み合わせたものであってもよい。
ここで、電子供与性の置換基(電子供与性基)とは、ハメット値(Hammett置換基定数σp)が0以下の置換基のことをいい、例えば、上述した置換基のうち、アルキル基、ハロゲン化アルキル基、アルコキシ基などが挙げられる。
これらのうち、アルコキシ基であることが好ましく、液晶配向性がより良好となる理由から、炭素数が6~16のアルコキシ基であることがより好ましく、炭素数7~10のアルコキシ基であることが更に好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、中でも、フッ素原子、塩素原子であるのが好ましい。
アルキル基としては、例えば、炭素数1~18の直鎖状、分岐鎖状または環状のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、シクロヘキシル基等)がより好ましく、炭素数1~4のアルキル基であることが更に好ましく、メチル基またはエチル基であるのが特に好ましい。
アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、メトキシエトキシ基等)がより好ましく、炭素数1~4のアルコキシ基であることが更に好ましく、メトキシ基またはエトキシ基であるのが特に好ましい。
アリール基としては、例えば、炭素数6~12のアリール基が挙げられ、具体的には、例えば、フェニル基、α-メチルフェニル基、ナフチル基などが挙げられ、中でも、フェニル基が好ましい。
アリールオキシ基としては、例えば、フェノキシ、ナフトキシ、イミダゾイルオキシ、ベンゾイミダゾイルオキシ、ピリジン-4-イルオキシ、ピリミジニルオキシ、キナゾリニルオキシ、プリニルオキシ、チオフェン-3-イルオキシなどが挙げられる。
アルコキシカルボニル基としては、例えば、メトキシカルボニル、エトキシカルボニルなどが挙げられる。
また、分岐状のアルキレン基としては、具体的には、例えば、ジメチルメチレン基、メチルエチレン基、2,2-ジメチルプロピレン基、2-エチル-2-メチルプロピレン基などが挙げられる。
また、環状のアルキレン基としては、具体的には、例えば、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロオクチレン基、シクロデシレン基、アダマンタン-ジイル基、ノルボルナン-ジイル基、exo-テトラヒドロジシクロペンタジエン-ジイル基などが挙げられ、中でも、シクロヘキシレン基が好ましい。
ここで、エチレン性不飽和二重結合を有する官能基としては、具体的には、例えば、ビニル基、アリル基、スチリル基、アクリロイル基、メタクリロイル基が挙げられ、アクリロイル基またはメタクリロイル基であることが好ましい。
0.03 ≦ a/(a+b) ≦ 0.5 ・・・(12)
0.03 ≦ a/(a+b) ≦ 0.3 ・・・(13)
0.03 ≦ a/(a+b) ≦ 0.2 ・・・(14)
0.05 ≦ a/(a+b) ≦ 0.2 ・・・(15)
0.05 ≦ b2/(a+b1+b2) ≦ 0.7 ・・・(16)
0.10 ≦ b2/(a+b1+b2) ≦ 0.5 ・・・(17)
このような他の繰り返し単位を形成するモノマー(ラジカル重合性単量体)としては、例えば、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリルアミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物、ビニル化合物等が挙げられる。
ここで、本発明における重量平均分子量および数平均分子量は、以下に示す条件でゲル浸透クロマトグラフ(GPC)法により測定された値である。
・溶媒(溶離液):THF(テトラヒドロフラン)
・装置名:TOSOH HLC-8320GPC
・カラム:TOSOH TSKgel Super HZM-H(4.6mm×15cm
)を3本接続して使用
・カラム温度:40℃
・試料濃度:0.1質量%
・流速:1.0ml/min
・校正曲線:TOSOH製TSK標準ポリスチレン Mw=2800000~1050(Mw/Mn=1.03~1.06)までの7サンプルによる校正曲線を使用
本発明に用いられる光吸収異方性層は、方向によって光吸収の程度が異なる層であって、通常、吸収軸と偏光軸(透過軸)とを有する。
また、本発明に用いられる光吸収異方性層は、二色性物質とともに液晶性化合物を含むことが好ましい。
また、本発明に用いられる光吸収異方性層は、二色性アゾ化合物を含むことが好ましい。
本発明に用いられる二色性物質は、特に限定されず、可視光吸収物質(二色性色素、二色性アゾ化合物)、発光物質(蛍光物質、燐光物質)、紫外線吸収物質、赤外線吸収物質、非線形光学物質、カーボンナノチューブ、無機物質(例えば量子ロッド)、などが挙げられ、従来公知の二色性物質(二色性色素)を使用することができる。また、液晶性を有する二色性物質も好ましい。
上記架橋性基としては、具体的には、例えば、(メタ)アクリロイル基、エポキシ基、オキセタニル基、スチリル基などが挙げられ、中でも、(メタ)アクリロイル基が好ましい。
本発明に用いられる液晶性化合物としては、低分子液晶性化合物および高分子液晶性化合物のいずれも用いることができる。
ここで、「低分子液晶性化合物」とは、化学構造中に繰り返し単位を有さない液晶性化合物のことをいう。
また、「高分子液晶性化合物」とは、化学構造中に繰り返し単位を有する液晶性化合物のことをいう。
また、高分子液晶性化合物は、末端に架橋性基(例えば、アクリロイル基およびメタクリロイル基)を有していてもよい。
ここで、重合性基としては、具体的には、例えば、(メタ)アクリロイル基、ビニル基、スチリル基、および、アリル基などが挙げられる。なかでも、(メタ)アクリロイル基が好ましい。
また、本発明においては、高分子液晶性化合物を含有していることが好ましく、高分子液晶性化合物とともに低分子液晶性化合物を併用することがより好ましい。
本発明に用いられる任意の硬化層は、厚み100nm以下の硬化層であることが好ましい。
硬化層としては、各種公知のものを使用できる。例えば、液晶性化合物を含む層や、多官能モノマーを含む組成物を硬化させた層があげられる。光吸収異方性層とインデックスマッチングを行えるような屈折率を有することが好ましい。
本発明に用いられる任意のポリビニルアルコール樹脂を含む層(PVA層)は、厚み2μm以下のポリビニルアルコール樹脂を含む層であることが好ましい。
本発明に用いられる任意の表面フィルムは、通常、得られる光学積層体中の最も外側に配置されることが好ましい。
表面フィルムとしては特に限定がなく、各種公知のものを使用できる。例えば、表面フィルムがハードコート層および基材を有する態様が挙げられる。
表面フィルムは、紫外線吸収剤を含んでいてもよい。
ハードコート層は、例えば、ハードコート層形成用組成物を基材上に塗布し、硬化させることによって形成できる。
また、他の機能を付加することを目的として、ハードコート層上に、他の機能層を積層してもよい。
また、ハードコート層にフィラーまたは添加剤を加えることで、機械的、電気的もしくは光学的な物理的な性能、または、撥水もしくは撥油性などの化学的な性能をハードコート層自体に付与できる。
ハードコート層は、耐擦傷性に優れるのが好ましい。具体的には、耐擦傷性の指標となる鉛筆硬度試験を実施した場合に、3H以上を達成するのが好ましい。
ハードコート層の厚みは、0.1~6μmが好ましく、3~6μmがより好ましい。
硬化性組成物は、液状の塗布組成物として調製されるのが好ましい。
硬化性組成物の一例は、マトリックス形成バインダー用モノマー、オリゴマー、または、ポリマーと、有機溶媒とを含む。
本発明に用いられる任意の位相差フィルムは、各種公知のものが利用できる。位相差フィルムの面内レタデーションの値は特に限定されず、位相差フィルムはλ/4板またはλ/2板であってもよい。また、複数層からなる位相差フィルムでもよい。
例えば、λ/4板が単層構造である態様としては、具体的には、延伸ポリマーフィルムや、支持体上にλ/4機能を有する光学異方性層を設けた位相差フィルムなどが挙げられ、また、λ/4板が複層構造である態様としては、具体的には、λ/4板とλ/2板とを積層してなる広帯域λ/4板が挙げられる。
本発明の画像表示装置は、上述した積層体と、画像表示素子とを含む。
本発明の画像表示装置に用いられる画像表示素子は特に限定されず、例えば、液晶セル、有機エレクトロルミネッセンス(以下、「EL」と略す。)表示パネル、および、プラズマディスプレイパネルなどが挙げられる。
これらのうち、液晶セルまたは有機EL表示パネルであるのが好ましく、液晶セルであるのがより好ましい。すなわち、本発明の画像表示装置としては、画像表示素子として液晶セルを用いた液晶表示装置、表示素子として有機EL表示パネルを用いた有機EL表示装置であるのが好ましく、有機EL表示装置であるのがより好ましい。
液晶表示装置に利用される液晶セルは、VA(Vertical Alignment)モード、OCB(Optically Compensated Bend)モード、IPS(In-Plane-Switching)モード、またはTN(Twisted Nematic)モードであることが好ましいが、これらに限定されるものではない。
TNモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に水平配向し、更に60~120゜にねじれ配向している。TNモードの液晶セルは、カラーTFT(Thin Film Transistor)液晶表示装置として最も多く利用されており、多数の文献に記載がある。
VAモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に垂直に配向している。VAモードの液晶セルには、(1)棒状液晶性分子を電圧無印加時に実質的に垂直に配向させ、電圧印加時に実質的に水平に配向させる狭義のVAモードの液晶セル(特開平2-176625号公報記載)に加えて、(2)視野角拡大のため、VAモードをマルチドメイン化した(MVAモードの)液晶セル(SID97、Digest of tech.Papers(予稿集)28(1997)845記載)、(3)棒状液晶性分子を電圧無印加時に実質的に垂直配向させ、電圧印加時にねじれマルチドメイン配向させるモード(n-ASMモード)の液晶セル(日本液晶討論会の予稿集58~59(1998)記載)および(4)SURVIVALモードの液晶セル(LCDインターナショナル98で発表)が含まれる。また、PVA(Patterned Vertical Alignment)型、光配向型(Optical Alignment)、およびPSA(Polymer-Sustained Alignment)のいずれであってもよい。これらのモードの詳細については、特開2006-215326号公報、および特表2008-538819号公報に詳細な記載がある。
IPSモードの液晶セルは、棒状液晶性分子が基板に対して実質的に平行に配向しており、基板面に平行な電界が印加することで液晶分子が平面的に応答する。IPSモードは電界無印加状態で黒表示となり、上下一対の偏光板の吸収軸は直交している。光学補償シートを用いて、斜め方向での黒表示時の漏れ光を低減させ、視野角を改良する方法が、特開平10-54982号公報、特開平11-202323号公報、特開平9-292522号公報、特開平11-133408号公報、特開平11-305217号公報、特開平10-307291号公報などに開示されている。
本発明の画像表示装置の一例である有機EL表示装置としては、例えば、視認側から、上述した本発明の積層体と、有機EL表示パネルと、をこの順で有する態様が好適に挙げられる。
より好適には、視認側から、λ/4板を有する上述した本発明の積層体と、有機EL表示パネルと、をこの順に有する態様である。この場合には、積層体は、視認側から、必要に応じて、表面フィルム、粘着層、光吸収異方性層、配向層、位相差フィルムの順に配置されている。
また、有機EL表示パネルは、電極間(陰極および陽極間)に有機発光層(有機エレクトロルミネッセンス層)を挟持してなる有機EL素子を用いて構成された表示パネルである。有機EL表示パネルの構成は特に制限されず、公知の構成が採用される。
<光配向層PA1の形成>
支持体として、TAC(トリアセチルセルロース)フィルム(TJ40UL、厚み40μm、富士フイルム社製)を用いた。
次いで、後述する配向層形成用組成物PA1を、ワイヤーバーで連続的に支持体上に塗布した。塗膜が形成された支持体を140℃の温風で120秒間乾燥し、続いて、塗膜に対して偏光紫外線照射(10mJ/cm2、超高圧水銀ランプ使用)することで、光配向層PA1を形成し、光配向層付きTACフィルムを得た。
なお、光配向層PA1の膜厚は1.0μmであった。
配向層形成用組成物PA1
─────────────────────────────────
・下記記重合体PA-1 100.00質量部
・下記酸発生剤PAG-1 5.00質量部
・下記酸発生剤CPI-110TF 0.005質量部
・キシレン 1220.00質量部
・メチルイソブチルケトン 122.00質量部
─────────────────────────────────
得られた光配向層PA1上に、下記組成の光吸収異方性層形成用組成物P1をワイヤーバーで連続的に塗布し、塗布層P1を形成した。
次いで、塗布層P1を140℃で90秒間加熱し、塗布層P1を室温(23℃)になるまで冷却した。
次いで、80℃で60秒間加熱し、再び室温になるまで冷却した。
その後、高圧水銀灯を用いて照度28mW/cm2の照射条件で60秒間照射することにより、光配向層PA1上に光吸収異方性層P1を形成した。
なお、光吸収異方性層P1の膜厚は0.4μmであった。
光吸収異方性層形成用組成物P1
――――――――――――――――――――――――――――――――
・下記アゾ色素Y-1 0.25質量部
・下記アゾ色素M-1 0.27質量部
・下記アゾ色素C-1 0.65質量部
・下記高分子液晶性化合物P-1 3.59質量部
・下記液晶化合物L-1 0.12質量部
・重合開始剤
IRGACUREOXE-02(BASF社製) 0.200質量部
・下記界面改良剤F-1 0.026質量部
・シクロペンタノン 47.50質量部
・テトラヒドロフラン 47.50質量部
――――――――――――――――――――――――――――――――
得られた光吸収異方性層P1上に、下記組成の硬化層形成用組成物L1をワイヤーバーで連続的に塗布し、組成物層L1を形成した。
次いで、組成物層L1を室温乾燥させ、次いで、高圧水銀灯を用いて照度28mW/cm2の照射条件で10秒間照射することにより、光吸収異方性層P1上に硬化層L1を形成した。
なお、硬化層L1の膜厚は、30nmであった。
――――――――――――――――――――――――――――――――
硬化層形成用組成物L1
――――――――――――――――――――――――――――――――
・下記棒状液晶性化合物の混合物L-2 2.43質量部
・下記変性トリメチロールプロパントリアクリレート 0.98質量部
・下記光重合開始剤I-1 0.20質量部
・上記界面改良剤F-1 0.14質量部
・1、4‐フェニレンジジボロン酸(東京化成工業) 0.10質量部
・メチルエチルケトン 371質量部
――――――――――――――――――――――――――――――――
硬化層L1上に、下記組成のポリビニルアルコール(PVA)層形成用塗布液B1をワイヤーバーで連続的に塗布した。
その後、100℃の温風で2分間乾燥することにより、硬化層L1上に厚み1.0μmのPVA層を形成した。
――――――――――――――――――――――――――――――――
PVA層形成用塗布液B1
――――――――――――――――――――――――――――――――
・下記の変性ポリビニルアルコール 3.80質量部
・開始剤Irg2959 0.20質量部
・水 70質量部
・メタノール 30質量部
――――――――――――――――――――――――――――――――
上記PVA層B1上に、以下で作製した粘着シートN1の粘着層N1側を圧着し、実施例1の積層体1を完成した。なお、粘着層の厚みは、20μmであった。
(粘着シートN1の作製)
攪拌機、温度計、還流冷却器および窒素導入管を備えた反応装置に、窒素ガスを導入して、この反応装置内の空気を窒素ガスに置換した。
その後、この反応装置中に、ブチルアクリレート70質量部、メチルアクリレート30質量部、アクリル酸4質量部、N,N-ジメチルメタクリルアミド2質量部、アゾビスイソブチロニトリル0.1質量部および酢酸エチル120質量部を加えた。
これを攪拌させながら、窒素ガス気流中において、60℃で8時間反応させ、重量平均分子量150万のアクリル系共重合体の溶液を得た。さらに酢酸エチルで希釈して固形分15%の共重合体溶液1を得た。
次いで、共重合体溶液1の固形分100質量部に対して、ポリイソシアネート(コロネートL、日本ポリウレタン工業社製)3質量部、アルミニウムトリスアセチルアセトネート(アルミキレートA、川研ファインケミカル社製)0.2質量部、および、γ-メルカプトプロピルメチルジメトキシシラン(KBM-803、信越化学工業社製)0.1質量部を混合した溶液(粘着剤組成物N1)を調製した。
次いで、調製した粘着剤組成物N1を、シリコーン樹脂コートされたPETフィルム(以下、「剥離フィルム」とも略す。)上に塗布し、90℃で乾燥することによって溶媒を除去し、厚さ20μmの粘着層N1を有する粘着シートN1を作製した。粘着層N1の貯蔵弾性率は、0.3MPaであった。
実施例1の光吸収異方性層の形成において、支持体をPET(厚み40μm)に変更した以外は、実施例1と同様の方法にて、実施例2の積層体を得た。
実施例1の光吸収異方性層の形成において、支持体をセルロースアシレートフィルムTJ100UL(厚み100μm、富士フイルム社製)に変更した以外は、実施例1と同様の方法にて、実施例3の積層体を得た。
実施例1の光吸収異方性層の形成において、光吸収異方性層形成用組成物、および、光配向層の厚みをそれぞれ下記表2に示すように変更した以外は、実施例1と同様の方法にて、実施例4~7の積層体を得た。
なお、下記表2中、光吸収異方性層形成用の組成物P2およびP3の詳細は、以下の通りである。
光吸収異方性層形成用組成物P2
――――――――――――――――――――――――――――――――
・上記アゾ色素Y-1 0.25質量部
・上記アゾ色素M-1 0.27質量部
・下記アゾ色素C-2 0.65質量部
・下記高分子液晶性化合物P-2 3.71質量部
・重合開始剤
IRGACUREOXE-03(BASF社製) 0.151質量部
・上記界面改良剤F-1 0.026質量部
・シクロペンタノン 47.50質量部
・テトラヒドロフラン 47.50質量部
――――――――――――――――――――――――――――――――
光吸収異方性層形成用組成物P3
――――――――――――――――――――――――――――――――
・下記アゾ色素Y-2 0.17質量部
・下記アゾ色素M-2 0.19質量部
・下記アゾ色素C-3 0.45質量部
・上記高分子液晶性化合物P-2 4.07質量部
・重合開始剤
IRGACUREOXE-03(BASF社製) 0.151質量部
・上記界面改良剤F-1 0.026質量部
・シクロペンタノン 47.50質量部
・テトラヒドロフラン 47.50質量部
――――――――――――――――――――――――――――――――
<光吸収異方性層P4の形成>
実施例1と同様の方法で、光配向層PA1を形成し、光配向層付きTACフィルムを得た。
得られた光配向層PA1上に、以下で調製した光吸収異方性層形成用組成物P4をワイヤーバーで連続的に塗布し、塗布層P4を形成した。
次いで、塗布層P4を120℃で60秒間加熱し、塗布層P4を室温(23℃)になるまで冷却した。
その後、高圧水銀灯を用いて照度28mW/cm2の照射条件で60秒間照射することにより、光配向層PA1上に光吸収異方性層P4を形成した。
なお、光吸収異方性層P4の膜厚は1.7μmであった。
――――――――――――――――――――――――――――――――
光吸収異方性層形成用組成物P4
――――――――――――――――――――――――――――――――
・下記アゾ色素Y-3 2.7質量部
・下記アゾ色素M-3 2.7質量部
・下記アゾ色素C-4 2.7質量部
・下記液晶化合物P-3 75.5質量部
・重合開始剤IRGACURE819(BASF社製) 0.8質量部
・上記界面改良剤F-1 0.6質量部
・シクロペンタノン 274.5質量部
・テトラヒドロフラン 640.5質量部
――――――――――――――――――――――――――――――――
上記光吸収異方性層P4上に、実施例1と同様にして、PVA層B1、粘着層を形成し、実施例8の積層体8を完成した。
実施例1の粘着層の形成において、上述した粘着シートN1および後述する粘着シートN2~N6における粘着層のうち、下記表2に示す粘着層を用い、下記表2に示す厚みに変更した以外は、実施例1と同様の方法にて、実施例9~16の積層体を得た。
粘着シートN1と同様にして、ブチルアクリレート95質量部、および、アクリル酸5質量部を溶液重合法により重合させて、平均分子量200万、分子量分布(Mw/Mn)3.0のアクリル系共重合体2を得た。
次いで、アクリル系共重合体2の固形分100質量部に対して、多官能アクリレート系モノマー(アロニックスM-315、東亜合成社製)10質量部、光重合開始剤(イルガキュア500、BASF社製)1質量部、トリメチロールプロパントリレンジイソシアネート(コロネートL、日本ポリウレタン社製)1質量部、および、シランカップリング剤(KBM-403、信越化学工業社製)0.2質量部を混合した溶液(粘着剤組成物N2)を調製した。
次いで、調製した粘着剤組成物N2を、シリコーン樹脂コートされたPETフィルム(剥離フィルム)上に塗布し、90℃で乾燥することによって溶媒を除去し、紫外線(UV)を下記条件で照射して、厚さ20μmの粘着層N2を有する粘着シートN2を作製した。粘着層N2の貯蔵弾性率は、0.6MPaであった。
(UV照射条件)
・フュージョン社無電極ランプ Hバルブ
・照度:600mW/cm2
・光量:150mJ/cm2
なお、UV照度および光量は、アイグラフィックス製「UVPF-36」を用いて測定した。
まず、以下の手順に従い、アクリル系ポリマーを調製した。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、2-エチルヘキシルアクリレート70質量部、アクリル酸エチル20質量部、ヒドロキシエチルメタクリレート6質量部、および、アクリル酸4質量部を溶液重合法により重合させて、平均分子量30万のアクリル系ポリマーA1を得た。
次に得られたアクリル系ポリマーA1を用いて、以下の手順に従い、粘着シートN3~N5を作製した。
具体的には、アクリル系ポリマーA1の固形分100質量部に対して、下記表1に示す質量部のトリメチロールプロパントリレンジイソシアネート(コロネートL、日本ポリウレタン社製)を添加し、粘着剤組成物を調製した。
次いで、調製した粘着剤組成物を、シリコーン樹脂コートされたPETフィルム(剥離フィルム)にダイコーターを用いて塗布し、150℃で3時間乾燥させ、所望の厚みの粘着層N3~5を有する粘着シートN3~5を作製した。粘着層N3~N5の貯蔵弾性率は、下記表1に示す通りであった、
粘着シートN2と同様にして、アクリル系共重合体2を得た。
次いで、アクリル系共重合体2の固形分100部に対して、トリメチロールプロパントリレンジイソシアネート(コロネートL、日本ポリウレタン社製)1質量部、および、シランカップリング剤(KBM-403、信越化学工業社製)0.2質量部を混合した溶液(粘着剤組成物N6)を調製した。
次いで、調製した粘着剤組成物N6を、シリコーン樹脂コートされたPETフィルム(剥離フィルム)上に塗布し、90℃で乾燥することによって溶媒を除去し、厚さ25μmの粘着層N6を有する粘着シートN6を作製した。粘着層N6の貯蔵弾性率は、0.1MPaであった。
支持体として、TJ40ULに代えてTJ100UL(厚み100μm、富士フイルム社製)を用いた以外は、実施例15と同様の方法にて、実施例17の積層体を得た。
粘着層の厚みを下記表2に示す値に変更した以外は、実施例10と同様の方法にて、比較例1の積層体を得た。
配向層形成用組成物PA1を下記組成の配向層形成用組成物PA2に変更した以外は、実施例1と同様の方法にて、比較例2の積層体を得た。
配向層形成用組成物PA2
─────────────────────────────────
・下記記重合体PA-2 100.00質量部
・上記酸発生剤PAG-1 5.00質量部
・上記酸発生剤CPI-110TF 0.005質量部
・キシレン 1220.00質量部
・メチルイソブチルケトン 122.00質量部
─────────────────────────────────
《剥離評価》
得られた積層体を25mm×150mmの大きさに裁断し、剥離フィルムを剥がした後、粘着層側をガラス基板(コーニング社Eagle XG)上に圧着した。
この後、積層体の支持体にテープを貼りつけて剥離した。
剥離した支持体の剥離面を観察し、以下の基準に沿って評価した。結果を下記表2に示す。
AA:剥離面の荒れ無し
A:剥離面がざらついている
B:配向層に起因する剥離残りが観察され、剥離面の面積に対する剥離残りの面積が5%未満
C:配向層に起因する剥離残りが観察され、剥離面の面積に対する剥離残りの面積が5%以上
また、配向層の形成に用いるシンナモイル化合物が、エチレン性不飽和二重結合を有する官能基を有していない場合、支持体のみを剥離することが困難であることが分かった(比較例2)。
これに対し、支持体および粘着層の厚みを除いた支持体から粘着層までの間の厚みが5μm以下である場合において、粘着層の厚みが5~50μmであり、配向層が、エチレン性不飽和二重結合を有する官能基を有するシンナモイル化合物を含有する配向層形成用組成物を用いて形成した光配向層であると、支持体を剥離することが容易であることが分かった(実施例1~17)。
2 配向層
3 光吸収異方性層
4 粘着層
5 硬化層
6 ポリビニルアルコール樹脂を含む層
7 表面フィルム
8 位相差フィルム
10 積層体
Claims (24)
- 支持体、配向層、光吸収異方性層、および、粘着層をこの順に有し、
前記支持体および前記粘着層を含まない前記支持体から前記粘着層までの間の厚みが5μm以下であり、
前記粘着層の厚みが、5μm~50μmであり、
前記配向層が、エチレン性不飽和二重結合を有する官能基を有するシンナモイル化合物を含有する配向層形成用組成物を用いて形成した光配向層である、積層体。 - 前記粘着層の貯蔵弾性率が、100kPa~20MPaである、請求項1に記載の積層体。
- 前記粘着層の貯蔵弾性率が、100kPa~2MPaである、請求項2に記載の積層体。
- 前記粘着層の厚みが、10μm超50μm以下である、請求項1~3のいずれか1項に記載の積層体。
- 前記光吸収異方性層が、二色性物質と液晶性化合物とを含む、請求項1~4のいずれか1項に記載の積層体。
- 前記光吸収異方性層が、二色性アゾ化合物を含む、請求項1~5のいずれか1項に記載の積層体。
- 前記光吸収異方性層の厚みが、0.1μm~3μmである、請求項1~6のいずれか1項に記載の積層体。
- 前記配向層の厚みが、0.1μm~2μmである、請求項1~7のいずれか1項に記載の積層体。
- 前記配向層の厚みが、0.5μm超2μm以下である、請求項8に記載の積層体。
- 前記シンナモイル化合物が、下記式(A)で表される光配向性基を含む繰り返し単位Aと、下記式(B)で表される架橋性基を含む繰り返し単位Bとを有する、光配向性共重合体である、請求項1~9のいずれか1項に記載の積層体。
前記式(B)中、R7は、水素原子またはメチル基を表し、L2は、2価の連結基を表し、Xは、下記式(X4)で表される架橋性基を表す。
- 前記液晶性化合物が、重合性液晶化合物である、請求項5に記載の積層体。
- 前記液晶性化合物が、高分子液晶性化合物である、請求項5に記載の積層体。
- 前記光吸収異方性層が、更に低分子液晶性化合物を含む、請求項13に記載の積層体。
- 前記光吸収異方性層と前記粘着層との間に、更に厚さ100nm以下の硬化層を有する、請求項1~14のいずれか1項に記載の積層体。
- 前記硬化層が液晶性化合物を含む、請求項15に記載の積層体。
- 前記硬化層が多官能モノマーを含む組成物を硬化させた層である、請求項15に記載の積層体。
- 前記光吸収異方性層と前記粘着層との間に、更に厚さ2μm以下のポリビニルアルコール樹脂を含む層を有する、請求項1~17のいずれか1項に記載の積層体。
- 前記支持体と前記配向層とが接している、請求項1~18のいずれか1項に記載の積層体。
- 前記配向層と前記光吸収異方性層とが接している、請求項1~19のいずれか1項に記載の積層体。
- 請求項1~20のいずれか1項に記載の積層体と、表面フィルムとを有し、前記粘着層と前記表面フィルムとが接している、積層体。
- 前記支持体が剥離された、請求項21に記載の積層体。
- 更に位相差フィルムを有し、前記位相差フィルムが前記配向層側に配置された、請求項22に記載の積層体。
- 請求項1~23のいずれか1項に記載の積層体と、画像表示素子とを有する、画像表示装置。
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