WO2022138925A1 - 波長選択吸収フィルタ及び表示装置 - Google Patents
波長選択吸収フィルタ及び表示装置 Download PDFInfo
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/003—Light absorbing elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/285—Interference filters comprising deposited thin solid films
- G02B5/287—Interference filters comprising deposited thin solid films comprising at least one layer of organic material
-
- 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
- G02F1/0009—Materials therefor
- G02F1/0063—Optical properties, e.g. absorption, reflection or birefringence
-
- 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
- G02F1/0102—Constructional details, not otherwise provided for in this subclass
- G02F1/0105—Illuminating devices
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/075—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00
- H01L25/0753—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00 the devices being arranged next to each other
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
-
- 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
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to a wavelength selective absorption filter and a display device.
- the display screen of the display is generally provided with an antireflection function so that the observer can easily see the image.
- an antireflection film or an antiglare film is realized by an antireflection film or an antiglare film.
- a general antireflection film a film having a refractive index different from that of the base material is coated on the surface of the base material, and the interference effect between the light reflected on the surface of the base material and the light reflected on the surface of the coated film causes.
- Examples thereof include an AR (Anti Reflection) film or an LR (Low Reflection) film that reduces reflection.
- AG AntiGlare
- an antiglare layer in which a film having a fine uneven pattern is coated on the surface of a base material and an image is prevented from being reflected by using a light scattering effect.
- Film is mentioned. However, a part of the light incident on the display passes through the antireflection film or the antiglare film on the surface and is reflected on the surface of the electrode or wiring or the glass surface of the cell. This is called internal reflection.
- the ratio of the area of the metal part such as the electrode or wiring to the total area of the panel increases, so that the internal reflection is prevented. Is a particularly important factor in ensuring high-quality display performance.
- a ⁇ / 4 retardation plate or a ⁇ / 2 retardation plate is provided between the polarizing element of the polarizing plate and the internal reflection portion, and circularly polarized light is provided.
- a method of making it function as a board is known.
- this method when the transmittance of the display light is reduced to about 40% and scattered particles are present between the circularly polarizing plate and the internal reflection point, polarization elimination occurs and a sufficient antireflection effect is obtained. There is a problem that it cannot be obtained.
- a liquid crystal display device using a method of preventing reflection of external light by adding an absorbent material of at least one of a material and a second absorbent material having a maximum absorbance in a wavelength band of 560 to 610 nm is disclosed. There is.
- Patent Document 3 for an image display device, particularly a self-luminous image display device such as a plasma display, in a wavelength region of 380 nm to 420 nm for the purpose of suppressing a decrease in contrast in a bright place and improving color reproduction. It has been proposed to use an optical filter having an absorption maximum in the wavelength region of 480 nm to 520 nm and the wavelength region of 585 nm to 620 nm, respectively.
- Patent Document 4 contains an absorbent material having an absorption maximum in the wavelength region of 380 nm to 420 nm, has selective absorption in the vicinity of 420 nm, and has a specific ratio of the absorbance at 450 nm to the absorbance at a wavelength of 420 nm.
- Optical films that are within range are listed.
- Patent Document 5 describes a cured film containing a dye having a specific chemical structure, and describes that the cured film has excellent blue light-cutting property.
- An object of the present invention is to provide a wavelength selective absorption filter exhibiting excellent light resistance and a display device including the same.
- an absorbent material having an absorption maximum in the wavelength region of 390 to 440 nm or an absorbent material having an absorption maximum in the wavelength region of 680 to 780 nm (a dye). It has been found that the dye) can sufficiently suppress the decrease in absorbance by containing a compound having a specific polar group, and is effective in improving the light resistance.
- a resin, a dye, and a compound having at least one polar group of a carboxylic acid ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a urethane bond, and a sulfonyl bond and having a molecular weight of 1000 or less are included.
- the dye comprises at least one of dye A and dye D shown below.
- the wavelength on the long wavelength side of the two wavelengths that give 20% absorbance with respect to the maximum absorbance at a wavelength of 390 to 440 nm is 455 nm or less.
- the wavelength on the short wavelength side of the two wavelengths that give 20% absorbance with respect to the maximum absorbance at a wavelength of 680 to 780 nm is 640 nm or more.
- Dye A Dye having a main absorption wavelength band at a wavelength of 390 to 440 nm
- Dye D Dye having a main absorption wavelength band at a wavelength of 680 to 780 nm ⁇ 2>
- ⁇ 3> The wavelength selective absorption filter according to ⁇ 1> or ⁇ 2>, wherein the dye A is a dye represented by the following general formula (A1).
- R 1 and R 2 each independently represent an alkyl group or an aryl group
- R 3 to R 6 each independently represent a hydrogen atom or a substituent
- R 5 and R 6 are bonded to each other. May form a 6-membered ring.
- ⁇ 4> The wavelength selective absorption filter according to any one of ⁇ 1> to ⁇ 3>, wherein the dye D is a squaric dye represented by the following general formula (1).
- G represents a heterocyclic group which may have a substituent.
- ⁇ 5> The wavelength selective absorption filter according to any one of ⁇ 1> to ⁇ 4>, wherein the compound having the above polar group is a compound having a carboxylic acid ester bond.
- ⁇ 6> The wavelength selection filter ⁇ 7> according to any one of ⁇ 1> to ⁇ 4>, wherein the compound having the above polar group is a compound having a carboxylic acid amide bond.
- ⁇ 8> The wavelength selective absorption filter according to any one of ⁇ 1> to ⁇ 6>, wherein the resin contains a cyclic polyolefin resin.
- ⁇ 10> The display device according to ⁇ 9>, wherein the display device is a self-luminous display device.
- substituents there is no particular notice when there are a plurality of substituents or linking groups (hereinafter referred to as substituents, etc.) represented by a specific code or formula, or when a plurality of substituents, etc. are specified at the same time. As long as each substituent or the like may be the same or different from each other. This also applies to the regulation of the number of substituents and the like. Further, when a plurality of substituents and the like are close to each other (particularly when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
- the ring for example, an alicyclic ring, an aromatic ring, or a heterocycle may be further condensed to form a fused ring.
- this carbon number means the carbon number of the entire group unless otherwise specified in the present invention or the present specification. That is, when this group is in the form of further having a substituent, it means the total number of carbon atoms including this substituent.
- one component die, resin, association inhibitor, other components, etc.
- the wavelength selective absorption filter may be contained in the wavelength selective absorption filter.
- two or more kinds may be contained.
- each component (crystalline resin or the like) constituting the gas barrier layer may be contained in the gas barrier layer, or two or more types may be contained in the gas barrier layer.
- the double bond may be any of E-type and Z-type in the molecule, or a mixture thereof.
- the indication of a compound (including a complex) is used to mean that the compound itself, its salt, and its ion are included. Further, it is meant to include a structure in which a part of the structure is changed as long as the effect of the present invention is not impaired. Further, the compound for which substitution or non-substitution is not specified may have any substituent as long as the effect of the present invention is not impaired.
- the numerical range represented by using "-" in the present invention means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the composition includes, in addition to a mixture having a constant component concentration (each component is uniformly dispersed), a mixture in which the component concentration fluctuates within a range that does not impair the desired function. do.
- having the main absorption wavelength band in the wavelength XX to YY nm means that the wavelength showing the maximum absorption (that is, the maximum absorption wavelength) exists in the wavelength region XX to YY nm.
- the entire absorption band including this wavelength may be within the wavelength region or may extend beyond the wavelength region. Further, when a plurality of maximum absorption wavelengths are present, it is sufficient that the maximum absorption wavelength showing the maximum absorbance exists in the above wavelength region. That is, the maximum absorption wavelength other than the maximum absorption wavelength showing the maximum absorbance may exist in or outside the wavelength region XX to YY nm.
- the main absorption wavelength band of the dye is the main absorption wavelength band of the dye measured in the state of the wavelength selective absorption filter.
- the measurement is performed in the state of the wavelength selective absorption filter under the conditions described in the section of the maximum absorbance value and the 20% value wavelength of the wavelength selective absorption filter.
- the maximum absorbance value at wavelengths XX to YY nm means the absorbance at the maximum absorption wavelength existing at the above wavelengths XX to YY nm, and is also referred to as an absorption maximum value.
- the two wavelengths that give 20% absorbance to the maximum absorbance at wavelengths XX to YY nm are the maximum absorption wavelengths that show the maximum absorbance at the absorption peak whose maximum absorbance is the maximum absorbance at wavelengths XX to YY nm.
- the wavelength located on the long wavelength side of the maximum absorption wavelength showing the maximum absorbance value is the wavelength located on the long wavelength side of the maximum absorption wavelength and showing the absorbance of 20% intensity of the maximum absorbance value. It means the wavelength of a short wave. Similarly, the wavelength located on the short wavelength side of the maximum absorption wavelength showing the maximum absorbance value is located on the short wavelength side of the maximum absorption wavelength and indicates the absorbance of 20% intensity of the maximum absorbance value. It means the wavelength of the longest wave.
- the maximum absorbance of the dye and the two wavelengths that give 20% absorbance to the maximum absorbance are values measured in the state of the wavelength selective absorption filter. Specifically, in the examples described later, the measurement is performed in the state of the wavelength selective absorption filter under the conditions described in the section of the maximum absorbance value and the 20% value wavelength of the wavelength selective absorption filter.
- the wavelength selective absorption filter of the present invention exhibits excellent light resistance. Further, the display device of the present invention includes the wavelength selective absorption filter having excellent light resistance.
- FIG. 1 is a schematic cross-sectional view showing an example of a laminated body including the wavelength selective absorption filter of the present invention.
- the wavelength selective absorption filter of the present invention (hereinafter, also referred to as a wavelength selective absorption layer) is at least one of a resin, a dye, a carboxylic acid ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a urethane bond and a sulfonyl bond. It contains a compound (association inhibitor) having one polar group (in the present invention, "group” means to include “bond”) and having a molecular weight of 1000 or less (association inhibitor), and the dye is in a different wavelength range. It contains at least one of the following dye A and dye D having a main absorption wavelength band.
- Dye A Dye having a main absorption wavelength band at a wavelength of 390 to 440 nm
- Dye D A dye having a main absorption wavelength band at a wavelength of 680 to 780 nm
- the wavelength selective absorption filter of the present invention may further contain at least one of the following dyes B and C.
- Dye B Dye having a main absorption wavelength band at a wavelength of 480 to 520 nm
- Dye C Dye having a main absorption wavelength band at a wavelength of 580 to 620 nm
- the "dye" is dispersed in the resin (dye). By dissolving (preferably), the wavelength selective absorption filter becomes a filter showing a specific absorption spectrum derived from the dye.
- the above dye A or dye D which has a main absorption wavelength band in a specific wavelength range, has many dyes in which association between molecules is likely to occur, and even in the form of a wavelength selective absorption filter dispersed (preferably dissolved) in a resin. , The dye is considered to exist in a state of being associated between molecules.
- the polarity of at least one of a carboxylic acid ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a urethane bond and a sulfonyl bond in addition to the resin and the dye containing at least one of the dye A and the dye D, the polarity of at least one of a carboxylic acid ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a urethane bond and a sulfonyl bond.
- the wavelength selective absorption filter of the present invention contains a dye containing at least one of dye A and dye D and the association inhibitor, and when dye A is contained, 20% of the absorbance of dye A at the maximum absorption wavelength.
- the wavelength on the long wavelength side showing the intensity of the dye D is adjusted to be 455 nm or less, and when the dye D is contained, the wavelength on the short wavelength side showing the intensity of 20% of the absorbance at the maximum absorption wavelength of the dye D is adjusted to be 640 nm or more. It is a wavelength selective absorption filter. By suppressing the association of the dye A or the dye D in this way, although it is presumed, the energy level of the excited state and the ground state of the dye changes, and the excited state can be quickly returned to the ground state. As a result, it is considered that the light resistance of the dye has been improved. As described above, since the wavelength selective absorption filter of the present invention has excellent light resistance, it can exhibit excellent light resistance even when applied to a display device.
- Patent Document 2 or 3 by applying a wavelength selective absorption filter adjusted with a dye to be contained to a display device, while exhibiting excellent light resistance, suppression of external light reflection and suppression of luminance decrease are suppressed. In addition, the influence on the color tone of the displayed image can be sufficiently suppressed.
- the wavelength selective absorption filter of the present invention is a filter (layer) containing at least one of the above dye A and dye D.
- the dye A contained in the wavelength selective absorption filter of the present invention may be one kind or two or more kinds.
- the wavelength selective absorption filter of the present invention contains the dye D
- the dye D contained in the wavelength selective absorption filter of the present invention may be one kind or two or more kinds.
- the dye B or the dye C that can be contained in the wavelength selective absorption filter of the present invention may be independently one kind or two or more kinds, respectively.
- the wavelength selective absorption filter of the present invention may also contain dyes other than the above dyes A to D.
- the form of the wavelength selective absorption filter of the present invention is such that the dye in the wavelength selective absorption filter can be sharpened by the association described later to show an absorption spectrum. It is preferable that both suppression of external light reflection and suppression of luminance decrease can be realized, and more preferably, it is sufficient as long as it does not easily affect the original color of the displayed image.
- the wavelength selective absorption filter of the present invention there is a form in which at least one of the dye A or the dye D is dispersed (preferably dissolved) in the resin. This variance may be random, regular, or the like.
- the dyes A to D are B (Blue, 440 nm to 470 nm), G (Green, 520 nm to 560 nm) and R (Red, 620 nm to) used as a light emitting source of the display device in the wavelength selective absorption filter of the present invention. It has a main absorption wavelength band in 390 to 440 nm, 480 to 520 nm, 580 to 620 nm, and 680 to 780 nm, which are wavelength ranges other than 660 nm) or wavelength ranges that do not largely overlap with these wavelength ranges.
- the wavelength selective absorption filter of the present invention emits light. It is possible to suppress the reflection of external light without impairing the color reproduction range of the light emitted from the element. Above all, it is preferable to contain both the dyes A and D from the viewpoint of adjusting the color of the reflected light.
- the wavelength selective absorption filter of the present invention can exhibit an excellent level of light resistance, which exceeds the decrease in light resistance due to the mixing of dyes, by providing a specific gas barrier layer described later. can.
- the wavelength selective absorption filter of the present invention contains dye A
- the wavelength on the long wavelength side of the two wavelengths that give 20% absorbance with respect to the maximum absorbance value at a wavelength of 390 to 440 nm is set to "20% value wavelength”. It is called "A”.
- the wavelength selective absorption filter of the present invention contains dye D
- the wavelength on the short wavelength side of the two wavelengths that give 20% absorbance to the maximum absorbance value at a wavelength of 680 to 780 nm is set to "20% value wavelength D.” Is called.
- the 20% value wavelength A is 455 nm or less
- the 20% value wavelength D is 640 nm or more.
- the 20% value wavelength A preferably satisfies the following relational expression (I)
- the 20% value wavelength D is the following relational expression from the viewpoint of achieving both antireflection and suppression of luminance reduction. It is preferable to satisfy (II).
- Relational expression (I) 410 nm ⁇ 20% value Wavelength A ⁇ 455 nm
- the upper limit of the 20% value wavelength A is preferably 453 nm or less, more preferably 450 nm or less.
- the lower limit is preferably 415 nm or more, more preferably 420 nm or more.
- the upper limit of the 20% value wavelength D is preferably 690 nm or less, more preferably 680 nm or less.
- the lower limit is preferably 645 nm or more, more preferably 650 nm or more.
- the dye A is not particularly limited as long as it has a main absorption wavelength band at a wavelength of 390 to 440 nm in the wavelength selective absorption filter, and various dyes can be used, and the wavelength is 395 to 430 nm in the wavelength selective absorption filter. Those having a main absorption wavelength band are preferable, and those having a main absorption wavelength band at a wavelength of 400 to 430 nm are more preferable.
- the dye A a dye represented by the following general formula (A1) is preferable because the absorption waveform in the main absorption wavelength band is sharp.
- R 1 and R 2 each independently represent an alkyl group or an aryl group
- R 3 to R 6 each independently represent a hydrogen atom or a substituent
- R 5 and R 6 respectively. May be coupled to each other to form a 6-membered ring.
- the alkyl group that can be taken as R 1 and R 2 may be any of an unsubstituted alkyl group and a substituted alkyl group having a substituent, either linear or branched, and may have a cyclic structure. good.
- Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a normal propyl group, an isopropyl group and a cyclohexyl group.
- the unsubstituted alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
- substituent group A Halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxyl group (may be in the form of salt), alkoxy group, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (in addition to -NH 2 , substitution represented by -NR a 2 ) Includes an amino group.
- Each R a independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, provided that at least one Ra is an alkyl group, an aryl group or a heteroaryl group).
- substituent group A preferable examples of the substituent that the substituted alkyl group can have include a halogen atom, an aryl group, an alkoxy group, an acyl group and a hydroxy group.
- the total number of carbon atoms of the substituted alkyl group is preferably 1 to 12.
- a benzyl group, a hydroxybenzyl group, a methoxyethyl group and the like can be mentioned.
- the total number of carbon atoms of the substituted alkyl group means the total number of carbon atoms of the substituted alkyl group including the substituents that the substituted alkyl group may have.
- it is used in the same meaning in other groups.
- R 1 and R 2 represent an alkyl group
- the alkyl groups may be the same or different.
- the aryl group that can be taken as R 1 and R 2 may be either an unsubstituted aryl group or a substituted aryl group having a substituent.
- the unsubstituted aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group.
- Examples of the substituent that the substituted aryl group can take include the substituent contained in the above-mentioned Substituent Group A.
- substituent group A preferable examples of the substituent that the substituted aryl group can have are a halogen atom (for example, a chlorine atom, a bromine atom and an iodine atom), a hydroxy group, a carboxy group, a sulfonamide group and an amino group.
- R a independently represents a hydrogen atom or an alkyl group. However, at least one Ra is an alkyl group. The number of carbon atoms is 1.
- an alkyl group preferably an alkyl group having 1 to 4 carbon atoms; for example, methyl, ethyl, normal propyl and isopropyl
- an alkoxy group preferably an alkoxy group having 1 to 4 carbon atoms; for example. , Methoxy, ethoxy, normal propoxy and isopropoxy
- alkoxycarbonyl groups preferably alkoxycarbonyl groups having 2-5 carbon atoms; eg, methoxycarbonyl, ethoxycarbonyl, normalpropoxycarbonyl and isopropoxycarbonyl
- sulfonyloxy groups preferably alkoxycarbonyl groups having 2-5 carbon atoms; eg, methoxycarbonyl, ethoxycarbonyl, normalpropoxycarbonyl and isopropoxycarbonyl
- a monovalent group in which at least two of these are linked can be mentioned.
- an aryl group having a total carbon number of 6 to 18 is preferable.
- Phenyl group 4- (2-hydroxyethoxy) phenyl group, N, N-dimethylaminophenyl group, 4- (N-carboxymethyl-N-ethylamino) phenyl group, 4-ethoxycarbonylphenyl group and 4-methanesulfonyl Oxyphenyl group is mentioned.
- R 1 and R 2 represent an aryl group
- the aryl groups may be the same or different.
- R 3 , R 4 , R 5 and R 6 examples include the substituents included in the above-mentioned substituent group A.
- R 3 , R 5 and R 6 are preferably an alkyl group or an aryl group. That is, it is preferable that R 3 , R 5 and R 6 are independently hydrogen atoms, alkyl groups or aryl groups, respectively.
- R4 is preferably an alkyl group or an aryl group. That is, R 4 is preferably a hydrogen atom, an alkyl group or an aryl group.
- the alkyl group that can be taken as R 3 , R 5 and R 6 may be any of an unsubstituted alkyl group and a substituted alkyl group having a substituent, and may be either linear or branched and has a cyclic structure. May be.
- Examples of the unsubstituted alkyl group that can be taken as R 3 , R 5 and R 6 include a methyl group, an ethyl group, a normal propyl group and an isopropyl group.
- the number of carbon atoms of the unsubstituted alkyl group that can be taken as R 3 , R 5 and R 6 is preferably 1 to 8, and more preferably 1 to 4.
- Examples of the substituent that the substituted alkyl group in R 3 , R 5 and R 6 may have include the substituent contained in the above-mentioned Substituent Group A.
- Preferred examples of the substituent that the substituted alkyl group in R 3 , R 5 and R 6 may have are an aryl group (preferably a phenyl group), a halogen atom, an acyl group, an amino group, an alkoxycarbonyl group, a carboxy group and a carboxy group. Hydroxyl groups can be mentioned.
- the total number of carbon atoms of the substituted alkyl group that can be taken as R 3 , R 5 and R 6 is preferably 1 to 8.
- a benzyl group, a carboxymethyl group and a hydroxymethyl group can be mentioned.
- R 3 , R 5 and R 6 all represent an alkyl group
- the alkyl groups may be the same or different.
- the aryl group that can be taken as R 3 , R 5 and R 6 may be either an unsubstituted aryl group or a substituted substituted aryl group.
- an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group.
- Examples of the substituent that the substituted aryl group in R 3 , R 5 and R 6 may have include the substituent contained in the above-mentioned Substituent Group A.
- Preferred examples of the substituent that the substituted aryl group in R 3 , R 5 and R 6 may have are a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a hydroxy group, a carboxy group, and a carboxy group.
- An alkyl group preferably an alkyl group having 1 to 4 carbon atoms; for example, methyl, ethyl, normal propyl and isopropyl).
- an aryl group having a total carbon number of 6 to 10 is preferable.
- 2-fluorophenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, hydroxyphenyl group, carboxyphenyl group, 3,5-dicarboxyphenyl group and 4-methylphenyl group can be mentioned.
- R 3 is preferably a hydrogen atom from the viewpoint of light resistance and heat resistance.
- R 3 , R 5 and R 6 are all aryl groups, the aryl groups may be the same or different.
- the alkyl group that can be taken as R 4 may be either an unsubstituted alkyl group or a substituted alkyl group having a substituent, may be linear or branched, and may have a cyclic structure.
- Examples of the unsubstituted alkyl group that can be taken as R4 include a methyl group, an ethyl group, a normal propyl group, an isopropyl group and a cyclohexyl group.
- the carbon number of the unsubstituted alkyl group that can be taken as R 4 is preferably 1 to 8, and more preferably 1 to 4.
- Examples of the substituent that the substituted alkyl group in R4 may have include the substituent contained in the above-mentioned Substituent Group A.
- Preferred examples of the substituent that the substituted alkyl group in R4 may have are an aryl group (preferably a phenyl group), a heterocyclic group, a carboxy group, a hydroxy group and an alkyl group (preferably having 1 to 4 carbon atoms).
- Alkyl group eg, methyl, ethyl, normal propyl and isopropyl
- alkoxy group preferably an alkoxy group having 1 to 4 carbon atoms; eg, methoxy, ethoxy, normal propoxy and isopropoxy
- aryloxy group alkoxycarbonyl group.
- an alkoxycarbonyl group having 2 to 5 carbon atoms for example, methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl and isopropoxycarbonyl
- an alkylamino group preferably an alkylamino group having 1 to 4 carbon atoms; for example, dimethyl
- alkylcarbonylamino group preferably an alkylcarbonylamino group having 1 to 4 carbon atoms; eg, a methylcarbonylamino group
- a cyano group e.g, an acyl group (eg, an acetyl group, a propionyl group, a benzoyl group, a mesyl group)
- acyl group eg, an acetyl group, a propionyl group, a benzoyl group, a mesyl group
- a monovalent group in which at least two of these are linked can be mentioned.
- the total number of carbon atoms of the substituted alkyl group that can be taken as R 4 is preferably 1 to 18.
- Methyl) Aminopropyl group and phenacyl group can be mentioned.
- the aryl group that can be taken as R 4 may be either an unsubstituted aryl group or a substituted aryl group having a substituent.
- an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group.
- Examples of the substituent that the substituted aryl group in R4 may have include the substituent contained in the above-mentioned Substituent Group A.
- Preferred examples of the substituent that the substituted aryl group in R4 may have are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), a hydroxy group, a carboxy group, a sulfonamide group, an amino group and an alkyl group (for example).
- an alkyl group having 1 to 4 carbon atoms for example, methyl, ethyl, normal propyl, isopropyl
- an alkoxy group preferably an alkoxy group having 1 to 4 carbon atoms; for example, methoxy, ethoxy, normal propoxy, isopropoxy
- An alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 5 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, normalpropoxycarbonyl, isopropoxycarbonyl
- a sulfonyloxy group preferably one in which at least two of these are linked. The basis of the price can be mentioned.
- the amino group that the substituted aryl group in R4 may have may be either an unsubstituted amino group (-NH 2 ) or a substituted amino group having a substituent (-NR a 2 in the substituent group A).
- a group similar to the substituted alkyl group in R 4 can be mentioned.
- the substituted amino group an alkylamino group in which one or two hydrogen atoms of the amino group are substituted with an alkyl group is preferable.
- alkylamino group examples include a methylamino group, a dimethylamino group, a diethylamino group and a pyrrolidino group.
- the number of carbon atoms of the alkylamino group is preferably 1 to 8, and more preferably 1 to 4.
- the alkyl group in the alkylamino group may be further substituted, and for example, a di (alkoxycarbonylalkyl) amino group is preferably mentioned.
- the di (alkoxycarbonylalkyl) amino group preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms.
- an aryl group having a total carbon number of 6 to 22 is preferable.
- R 5 and R 6 may be coupled to each other to form a 6-membered ring. Hydrogen atoms may be desorbed during the formation of the ring to form an aromatic ring or an aliphatic ring having an unsaturated bond.
- the 6-membered ring formed by bonding R 5 and R 6 to each other is preferably a benzene ring.
- R 1 and R 2 in the general formula (A1) it is preferable that R 1 is an alkyl group, R 1 is an alkyl group, and R 2 is an alkyl group or aryl. It is more preferable that it is a group. From the same viewpoint, it is more preferable that both R 1 and R 2 are independently alkyl groups, and it is particularly preferable that they are alkyl groups having 1 to 8 carbon atoms.
- both R 1 and R 2 in the general formula (A1) are aryl groups.
- R 1 and R 2 each independently represent an aryl group
- R 3 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group or an aryl group and at least R 3 and R 6 .
- One is preferably a hydrogen atom.
- R 3 represents a hydrogen atom and R 5 and R 6 each independently represent an alkyl group or an aryl group, and R 3 represents a hydrogen atom and R 5 It is more preferable that and R 6 each independently represent an alkyl group, R 3 represents a hydrogen atom, R 5 and R 6 each independently represent an alkyl group, and R 5 and R 6 are bonded to each other. It is particularly preferable that a ring is formed and condensed with a pyrrole ring to form an indole ring together with the pyrrol ring. That is, the dye represented by the general formula (A1) is particularly preferably a dye represented by the following general formula (A2).
- R 1 to R 4 have the same meaning as R 1 to R 4 in the general formula (A1), and the preferred embodiments are also the same.
- R 15 represents a substituent.
- the substituent that can be taken as R 15 include the substituents included in the above-mentioned substituent group A.
- R15 an alkyl group, an aryl group, a halogen atom, an acyl group, an amino group or an alkoxycarbonyl group is preferable.
- the alkyl group and aryl group that can be taken as R 15 the description of the alkyl group and aryl group that can be taken as R 3 , R 5 and R 6 can be applied, respectively.
- the halogen atom that can be taken as R 15 include a chlorine atom, a bromine atom and an iodine atom.
- Examples of the acyl group that can be taken as R15 include an acetyl group, a propionyl group and a butyroyl group.
- the amino group that can be taken as R 15 the description of the amino group that the substituted aryl group in R 4 can have can be applied.
- a nitrogen-containing heterocyclic group having a 5- to 7-membered ring in which an alkyl group on the nitrogen atom of the amino group is bonded to form a ring is also preferable.
- the alkoxycarbonyl group that can be taken as R15 is preferably an alkoxycarbonyl group having 2 to 5 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl and isopropoxycarbonyl.
- N is an integer from 0 to 4.
- n is not particularly limited, but is preferably 0 or 1, for example.
- the dye A in addition to the dye represented by the general formula (A1), the compounds described in paragraphs [0012] to [0067] of JP-A-5-53241, and paragraph [0011] of Japanese Patent No. 2707371. ] To [0076] can also be preferably used.
- the dye B is not particularly limited as long as it has a main absorption wavelength band at a wavelength of 480 to 520 nm in the wavelength selective absorption filter, and various dyes can be used.
- the dye C is not particularly limited as long as it has a main absorption wavelength band at a wavelength of 580 to 620 nm in the wavelength selective absorption filter, and various dyes can be used.
- the dye B include, for example, pyrrole methine (PM) -based, rhodamine (RH) -based, boron dipyrromethene (BODIPY) -based and squaric (squarine, SQ) -based dyes.
- Specific examples of the dye C include tetraaza porphyrin (TAP) -based, squaric-based and cyanine (CY) -based dyes (dye).
- a squaric dye is preferable because the absorption waveform in the main absorption wavelength band is sharp, and it is referred to in International Publication No. 2019/189463 [0016] to [0070].
- the squaric dye represented by the general formula (1) described above is more preferable.
- a dye having a sharp absorption waveform as described above as the dye B and the dye C both the reflectance and the suppression of the decrease in luminance can be achieved at the same time. That is, in the wavelength selective absorption filter of the present invention, from the viewpoint of suppressing the above-mentioned color change, at least one of the dye B and the dye C is a squaric dye (preferably, International Publication No.
- the dye is a squaric dye represented by the general formula (1) described in [0070], and both the dye B and the dye C are squaric dyes (preferably, International Publication No. 2019/189463 [0016]. It is more preferable that it is a squaric dye represented by the general formula (1) described in [0070].
- the description of dye A in International Publication No. 2019/189463 shall be read as dye B in the present invention, and the description of dye B in International Publication No. 2019/189463 shall be read as dye C in the present invention.
- the squaric dye represented by the general formula (1) described in International Publication No. 2019/189463 is a quencher-embedded dye in which the quencher portion is linked to the dye by a covalent bond via a linking group. You may.
- the quencher-embedded dye can also be preferably used as at least one of the dyes B and C. That is, the quencher-embedded dye is counted as dye B or dye C depending on the wavelength having the main absorption wavelength band. Examples of the quencher unit include a metallocenyl group in the substituent X described later.
- the dye D is not particularly limited as long as it has a main absorption wavelength band at a wavelength of 680 to 780 nm in the wavelength selective absorption filter, and various dyes can be used.
- dye D examples include porphyrin-based, squaric-based, and cyanine (CY) -based dyes.
- the dye D a squaric dye is preferable because the absorption waveform in the main absorption wavelength band is sharp, and a squaric dye represented by the following general formula (1) is more preferable.
- the cation exists in a delocalized manner, and a plurality of tautomer structures exist. Therefore, in the present invention, when at least one tautomeric structure of a certain dye applies to each general formula, the certain dye is a dye represented by each general formula. Therefore, the dye represented by a specific general formula can also be said to be a dye whose at least one tautomer structure can be represented by a specific general formula.
- the dye represented by the general formula may have any tautomeric structure as long as at least one of the tautomer structures applies to this general formula.
- G represents a heterocyclic group which may have a substituent.
- the aryl group that can be taken as A or B is not particularly limited, and may be a group composed of a monocyclic ring or a group composed of a condensed ring.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
- Examples of the aryl group include groups composed of a benzene ring or a naphthalene ring, and a group composed of a benzene ring is preferable.
- the heterocyclic group that can be taken as A or B is not particularly limited, and includes a group composed of an aliphatic heterocycle or an aromatic heterocycle, and a group composed of an aromatic heterocycle is preferable.
- Examples of the heteroaryl group which is an aromatic heterocyclic group include a heteroaryl group which can be taken as the substituent X described later.
- the aromatic heterocyclic group that can be taken as A or B is preferably a 5-membered ring or a 6-membered ring group, and more preferably a nitrogen-containing 5-membered ring group.
- a group consisting of any of a ring, a benzoxazole ring and a pyrazolotriazole ring is preferably mentioned.
- a group consisting of any of a pyrrole ring, a pyrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring and a pyrazorotriazole ring is preferable.
- the pyrazolotriazole ring is composed of a fused ring of a pyrazole ring and a triazole ring, and may be a fused ring formed by condensing at least one of these rings.
- a pyrazole ring and a triazole ring are one. Examples thereof include a fused ring in the form of forming a fused ring in a form that shares a nitrogen atom and one carbon atom.
- a and B may be bonded to the squaric acid moiety (the 4-membered ring represented by the general formula (1)) at any moiety (ring-constituting atom) without particular limitation, but carbon. It is preferable to bond with an atom.
- G represents a heterocyclic group which may have a substituent, for example, the example shown in the above-mentioned heterocyclic group which can be taken as A or B. Preferred. Among them, a group composed of any one of a benzoxazole ring, a benzothiazole ring and an indoline ring is preferable.
- At least one of A and B may have a hydrogen-bonding group that forms an intramolecular hydrogen bond.
- Each of A, B and G may have a substituent X, and when it has a substituent X, adjacent substituents may be bonded to each other to further form a ring structure. Further, a plurality of substituents X may be present. When adjacent substituents X are bonded to each other to further form a ring structure, the two substituents X may form a ring with a hetero atom such as a boron atom interposed therebetween. This boron atom may be further substituted with a substituent, and examples thereof include substituents such as an alkyl group and an aryl group.
- a ring formed by bonding two substituents X for example, a ring formed by bonding two following-NR 14 R 15s and two following -NR 14 R 15 sandwiching a boron atom.
- substituent X include the following groups. Alkyl group (carbon number is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8. For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, octyl.
- An alkenyl group (the number of carbon atoms is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, for example, vinyl, allyl),.
- An alkynyl group (the number of carbon atoms is preferably 2 to 40, more preferably 2 to 30, particularly preferably 2 to 25, for example, ethynyl, propargyl),.
- Aryl groups (the number of carbon atoms is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 12, for example, phenyl, naphthyl.),.
- Heterocyclic group (including aromatic heterocyclic group and aliphatic heterocyclic group.
- a group consisting of a monocyclic or fused ring, and a monocyclic or a group consisting of a fused ring having 2 to 8 rings is preferable.
- a group consisting of a ring or a fused ring having 2 to 4 rings is more preferable.
- the number of hetero atoms constituting the ring is preferably 1 to 3, and the hetero atom constituting the ring is a nitrogen atom, an oxygen atom or a sulfur atom.
- the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
- the carbon number of the aralkyl group is preferably 7 to 40, preferably 7 to 30. More preferably, 7 to 25 is even more preferable), Metallocenyl group, -OR 10 (for example, hydroxy group, alkoxy group (methoxy, ethoxy, propyloxy, etc.), cycloalkoxy group (cyclopentyloxy, cyclohexyloxy, etc.), aryloxy group (phenoxy, naphthyloxy, etc.), heteroaryloxy group (aromatic) Group heterocyclic oxy group)),.
- Metallocenyl group, -OR 10 for example, hydroxy group, alkoxy group (methoxy, ethoxy, propyloxy, etc.), cycloalkoxy group (cyclopentyloxy, cyclohexyloxy, etc.), aryloxy group (phenoxy, naphthyloxy, etc.), heteroaryloxy group (aromatic) Group heterocyclic oxy group)),.
- R 11 acyl groups such as acetyl, ethylcarbonyl, propylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl and the like),.
- OR 12 for example, carboxy group, alkoxycarbonyl group (methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl group (phenyloxycarbonyl, naphthyloxycarbonyl, etc.)) Is mentioned.
- -OC ( O)
- R 13 includes acyloxy groups such as acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, and phenylcarbonyloxy),.
- -NR 14 R 15 (Amino groups such as amino (-NH 2 ), ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.
- -NHCOR 16 methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.
- -CONR 17 R 18 aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl , 2-Pyridylaminocarbonyl and the like carboxamide groups.
- -NHCONR 19 R 20 including ureido groups such as methyl ureido, ethyl ureido, pentyl ureido, cyclohexyl ureido, octyl ureido, dodecyl ureido, phenyl ureido, naphthyl ureido,
- -NHCOOR 21 , -SR 22 for example, alkylthio group (methyl thio, ethylthio, propylthio, etc.), cycloalkylthio group (cyclopentylthio, cyclohexylthio, etc.), arylthio group (phenylthio, naphthylthio, etc.), heteroarylthio group (aromatic heterocyclic thio group) Is mentioned.), -SO 2 R 23 (for example, an alkyl sulfonyl group (methyl sulfonyl, ethyl sulfonyl, butyl sulfonyl, cyclohexyl sulfonyl, 2-ethylhexyl sulfonyl, etc.), aryl sulfonyl (phenyl sulfonyl, naphthyl sulfonyl, 2-pyridyl
- -OSO 2 R 24 Alkylsulfonyloxy groups such as methanesulfonyloxy can be mentioned
- -NHSO 2 R 25 including sulfonylamide groups such as methylsulfonylamino, octylsulfonylamino, 2-ethylhexylsulfonylamino, trifluoromethylsulfonylamino
- -SO 2 NR 26 R 27 (Sulfamoyl groups such as aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl),.
- the substituent X has the above-mentioned quenching agent portion in addition to the above-mentioned metallocenyl group.
- each of R 10 to R 28 independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
- the aliphatic group and aromatic group that can be taken as R 10 to R 28 are not particularly limited, and the alkyl group, the alkenyl group and the alkynyl group classified as the aliphatic group in the substituent that can be taken as the substituent X are also used. , Can be appropriately selected from aryl groups classified as aromatic groups.
- the heterocyclic group that can be taken as R 10 to R 28 may be an aliphatic or aromatic group, and is appropriately selected from, for example, a heterocyclic group (aromatic heterocyclic group or an aliphatic heterocyclic group) that can be taken as the substituent X.
- a heterocyclic group aromatic heterocyclic group or an aliphatic heterocyclic group
- the alkyl group, alkenyl group and alkynyl group which can be taken as the substituent X may be linear, branched or cyclic, respectively, and linear or branched is preferable.
- R 12 of ⁇ COOR 12 is a hydrogen atom (that is, a carboxy group)
- the hydrogen atom may be dissociated (that is, a carbonate group) or may be in a salt state.
- R 24 of —OSO 2 R 24 is a hydrogen atom (that is, a sulfo group)
- the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.
- the substituent that can be taken as the substituent X may further have a substituent.
- examples of the substituent that may be possessed include the above-mentioned substituent X.
- adjacent substituents may be bonded to each other to form a ring, and the formed ring is preferably an aliphatic heterocycle or a heteroaryl ring, and the size of the formed ring is not particularly limited. It is preferably a 5-membered ring or a 6-membered ring. Further, the number of rings formed is not particularly limited, and may be one or two or more.
- the metallocenyl group that can be taken as the substituent X is preferably represented by the following general formula (2M).
- L represents a single bond or a divalent linking group that is not conjugate with A, B or G in the general formula (1).
- R1m to R9m represent hydrogen atoms or substituents, respectively.
- M is an atom that can constitute a metallocene compound, and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V or Pt. * Indicates a joint with A, B or G.
- L in the general formula (2M) is a single bond, a cyclopentadienyl ring directly bonded to A, B or G (a ring having R 1m in the general formula (2M)). Is not included in the conjugated structure coupled with A, B or G.
- the divalent linking group that can be taken as L is not particularly limited as long as it is a linking group that does not conjugate with A, B or G, and is described above at the inside thereof or at the cyclopentadiene ring side end portion in the general formula (2M). May include a conjugate structure of.
- -CO-, -CS-, -NR- R indicates a hydrogen atom or a monovalent substituent
- R indicates a hydrogen atom or a monovalent substituent
- -O-, -S-, -SO2- or -N CH-, or these.
- Examples thereof include a divalent linking group consisting of a plurality (preferably 2 to 6) in combination.
- the combined divalent linking group is not particularly limited, but a group containing -CO-, -NH-, -O- or -SO2- is preferable, and -CO-, -NH-, -O- or- Examples thereof include a linking group consisting of two or more SO 2- or a combination of at least one of -CO-, -NH-, -O- and -SO 2- and an alkylene group or an arylene group. Be done.
- linking group consisting of two or more combinations of -CO-, -NH-, -O- or -SO 2- , -COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, -SO 2 NH- is mentioned.
- the linking group consisting of a combination of at least one of -CO-, -NH-, -O- and -SO 2- and an alkylene group or an arylene group includes -CO-, -COO- or -CONH- and an alkylene. Examples thereof include a group in combination with a group or an arylene group.
- the substituent that can be taken as R is not particularly limited and has the same meaning as the above-mentioned substituent X.
- L may have one or more substituents.
- the substituent that L may have is not particularly limited, and is synonymous with, for example, the above-mentioned substituent X.
- the substituents bonded to adjacent atoms may be bonded to each other to further form a ring structure.
- the alkylene group that can be taken as L may be linear, branched or cyclic as long as it is a group having 1 to 20 carbon atoms, and for example, methylene, ethylene, propylene, methylethylene, methylmethylene, etc.
- the group such as —CO— may be incorporated at any position in the alkylene group, and the number of incorporated groups is not particularly limited.
- the arylene group that can be taken as L is not particularly limited as long as it is a group having 6 to 20 carbon atoms, and for example, an aryl group having 6 to 20 carbon atoms that can be taken as A in the general formula (1). Examples thereof include groups in which one hydrogen atom is further removed from each group exemplified as.
- the heterocyclic group that can be taken as L is not particularly limited, and examples thereof include a group obtained by further removing one hydrogen atom from each group exemplified as the heterocyclic group that can be taken as A.
- the remaining partial structure excluding the linking group L corresponds to a structure (metallocene structure portion) in which one hydrogen atom is removed from the metallocene compound.
- the metallocene compound serving as the metallocene structure is a known metallocene compound as long as it is a compound conforming to the partial structure defined by the above general formula (2M) (a compound in which a hydrogen atom is bonded instead of L). It can be used without particular limitation.
- the metallocene structure defined by the general formula (2M) will be specifically described.
- R 1m to R 9m represent hydrogen atoms or substituents, respectively.
- the substituent that can be taken as R 1 m to R 9 m is not particularly limited, but can be selected from, for example, the substituent that can be taken as the above-mentioned Substituent X.
- R 1m to R 9m are preferably a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group or an amide group, respectively, and more preferably a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an alkoxy group.
- a hydrogen atom, a halogen atom, an alkyl group or an acyl group is more preferable, a hydrogen atom, a halogen atom or an alkyl group is particularly preferable, and a hydrogen atom is the most preferable.
- an alkyl group having 1 to 8 carbon atoms is preferable, and for example, methyl, ethyl, propyl, isopropyl, butyl, sec- Examples thereof include butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, octyl and 2-ethylhexyl.
- This alkyl group may have a halogen atom as a substituent.
- Alkyl groups substituted with halogen atoms include, for example, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl. , Perfluoroethyl, perfluoropropyl, perfluorobutyl and the like. Further, in the alkyl group that can be taken as R 1 m or the like, at least one methylene group forming a carbon chain may be substituted with —O— or —CO—.
- alkyl group in which the methylene group is substituted with —O— examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, third butoxy, 2-methoxyethoxy, chloromethyloxy, dichloromethyloxy and trichloro.
- Methyloxy bromomethyloxy, dibromomethyloxy, tribromomethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, 2,2,2-trifluoroethyloxy, perfluoroethyloxy, perfluoropropyloxy, Examples thereof include an alkyl group in which the end methylene group of perfluorobutyloxy is substituted, an alkyl group in which the internal methylene group of the carbon chain such as 2-methoxyethyl is substituted, and the like.
- Alkyl groups in which the methylene group is substituted with -CO- include, for example, acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propane-2-one-1-yl, butane-2-one-. 1-Il and the like can be mentioned.
- M is an atom that can constitute a metallocene compound, and is Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh. , V or Pt.
- M is preferably Fe, Ti, Co, Ni, Zr, Ru or Os, more preferably Fe, Ti, Ni, Ru or Os, further preferably Fe or Ti, and most preferably Fe.
- a group formed by combining preferable groups of L, R 1m to R 9m and M is preferable, and for example, as L, a single bond or a group having 2 to 8 carbon atoms is preferable.
- a group formed by combining with Fe can be mentioned.
- the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group which can be taken as the substituent X, and the aliphatic group, aromatic group and heterocyclic group which can be taken as R10 to R28 are each. Further, it may have a substituent or may be unsubstituted. Further, the substituent which may be possessed is not particularly limited, but is limited to an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group and an aryloxy group.
- the dye D is a dye represented by the general formula (1), it is preferably a dye represented by the following general formula (14).
- R 1 and R 2 each independently represent a hydrogen atom or a substituent.
- R 1 and R 2 may be the same or different from each other, or may be combined with each other to form a ring.
- the substituents that can be taken as R 1 and R 2 are not particularly limited, but for example, the alkyl group (including the cycloalkyl group), the alkenyl group, the alkynyl group, the aryl group and the heterocyclic group (fragrance) in the above-mentioned substituent X are not particularly limited.
- alkoxy group (Including group heterocyclic group and aliphatic heterocyclic group), alkoxy group, cycloalkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, cycloalkylthio group, arylthio group, heteroarylthio group, alkoxycarbonyl group, aryl Oxycarbonyl group, phosphoryl group, sulfamoyl group, acyl group, acyloxy group, amide group, sulfonylamide group, carbamoyl group, ureido group, alkylsulfonyl group, arylsulfonyl group, amino group, alkylsulfonyloxy group, cyano group, nitro group , Halogen atom, hydroxy group and the like.
- R 41 and R 42 are also synonymous with the above-mentioned R 1 and R 2 .
- R 1 , R 2 , R 41 and R 42 may further have a substituent.
- examples of the substituent that may be possessed include the above-mentioned substituent X.
- an alkyl group, an alkenyl group, an aryl group or a heteroaryl group is preferable, an alkyl group, an aryl group or a heteroaryl group is more preferable, and an alkyl group or an aryl group is further preferable. preferable.
- B 1 , B 2 , B 3 and B 4 in the general formula (14) each independently represent a carbon atom or a nitrogen atom.
- the ring containing B 1 , B 2 , B 3 and B 4 is an aromatic ring.
- B 1 to B 4 at least two or more are preferably carbon atoms, and it is more preferable that all of B 1 to B 4 are carbon atoms.
- the carbon atom that can be taken as B 1 to B 4 has a hydrogen atom or a substituent.
- the number of carbon atoms having a substituent is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1.
- B 1 and B 4 are carbon atoms and at least one of them has a substituent.
- the substituents contained in the carbon atoms that can be taken as B 1 to B 4 are not particularly limited, and examples thereof include the above-mentioned substituents that can be taken as R 1 and R 2 .
- a hydroxy group more preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amide group, a sulfonylamide group, a carbamoyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxy group.
- B 5 , B 6 , B 7 and B 8 are synonymous with the above B 1 , B 2 , B 3 and B 4 , respectively.
- the substituents of the carbon atoms that can be taken as B 1 to B 8 may further have a substituent. Further, examples of the substituent that may be possessed include the above-mentioned substituent X.
- an alkyl group, an alkoxy group, a hydroxy group, an amide group, a sulfonylamide group or a carbamoyl group is more preferable, and an alkyl group is particularly preferable.
- Examples thereof include a group, an alkoxy group, a hydroxy group, an amide group or a sulfonylamide group, and most preferably a hydroxy group, an amide group or a sulfonylamide group.
- an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an amino group, a cyano group, a nitro group or a halogen atom is more preferable.
- one of the substituents is an electron-attracting group (for example, an alkoxycarbonyl group, an acyl group, a cyano group, a nitro group or a halogen atom).
- R 1 and R 2 may be bonded to each other to form a ring, and R 1 or R 2 may be bonded to the substituent of B 2 or B 3 to form a ring. You may. Further, R 41 and R 42 may be bonded to each other to form a ring, or R 41 or R 42 may be bonded to the substituent of B 6 or B 7 to form a ring.
- the ring formed is preferably a heterocycle or a heteroaryl ring, and the size of the formed ring is not particularly limited, but a 5-membered ring or a 6-membered ring is preferable. Further, the number of rings formed is not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include a form in which the substituents of R 1 and B 2 and the substituents of R 2 and B 3 are bonded to each other to form two rings. Can be mentioned.
- dye D A specific example of dye D is shown below.
- the following compounds F-1 to F-33 are dyes represented by the general formula (1).
- the total content of the dyes A to D in the wavelength selective absorption filter of the present invention is not particularly limited as long as the effect of the present invention is exhibited, and is preferably 0.01% by mass or more, preferably 0.05% by mass or more. Is more preferable, 0.10% by mass or more is further preferable, 0.15% by mass or more is particularly preferable, and 0.20% by mass or more is particularly preferable.
- the total content of the dyes A to D in the wavelength selective absorption filter of the present invention is usually 70% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
- the content of each of the dyes A to D that can be contained in the wavelength selective absorption filter of the present invention is preferably as follows.
- the content of the dye A in the wavelength selective absorption filter of the present invention is preferably 0.01 to 45% by mass, more preferably 0.1 to 30% by mass.
- the content of the dye B in the wavelength selective absorption filter of the present invention is preferably 0.01 to 45% by mass, more preferably 0.1 to 30% by mass.
- the content of the dye C in the wavelength selective absorption filter of the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 25% by mass.
- the content of the dye D in the wavelength selective absorption filter of the present invention is preferably 0.01 to 45% by mass, more preferably 0.1 to 30% by mass.
- the content of the quencher-embedded dye in the wavelength selective absorption filter of the present invention is 0.1 from the viewpoint of the antireflection effect. It is preferably mass% or more. The upper limit is preferably 45% by mass or less.
- the resin contained in the wavelength selective absorption filter of the present invention can disperse (preferably dissolve) the above dye and the association inhibitor described later, and the association of the dye by the association inhibitor. Is not particularly limited as long as it can suppress the decrease in light resistance and suppress the decrease in light resistance. It is preferable that the suppression of external light reflection and the suppression of luminance decrease can be satisfied, and the original color of the image of the display device (preferably a self-luminous display device) can be maintained at an excellent level.
- the matrix resin is a low-polarity matrix resin capable of exhibiting sharper absorption of the squaric dye. Is preferable.
- squaric dye represented by the general formula (1) described in International Publication No. 2019/189463 is contained as at least one of the dyes B or C. Since the above-mentioned squaric dye exhibits sharper absorption, it is possible to achieve both antireflection and suppression of luminance decrease at an excellent level.
- low polarity means that the fd value defined by the following relational expression ⁇ is preferably 0.50 or more.
- Relational expression ⁇ : fd ⁇ d / ( ⁇ d + ⁇ p + ⁇ h)
- ⁇ , ⁇ d, ⁇ p, and ⁇ h correspond to the London dispersion force, the dipole intermolecular force, and the hydrogen bond force with respect to the solubility parameter ⁇ t calculated by the Hoy method, respectively. Indicates a term. The specific calculation method will be described later. That is, fd indicates the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h. By setting the fd value to 0.50 or more, it becomes easier to obtain a sharper absorption waveform.
- the fd value is calculated as follows.
- fd ⁇ ( wi ⁇ fd i )
- wi indicates the mass fraction of the i -th matrix resin
- fdi indicates the fd value of the i -th matrix resin.
- ⁇ d corresponding to the London dispersion force The term ⁇ d corresponding to the London dispersion force is obtained for the Amorphous Polymers described in the column “2) Method of Hoy (1985, 1989)” on pages 214 to 220 of the document “Properties of Polymers 3rd, ELSEVIER , (1990)”. ⁇ d, which is calculated according to the description in the above column of the above document.
- ⁇ p corresponding to the dipole intramolecular force refers to the Amorphous Polymers described in the “2) Method of Hoy (1985, 1989)” column of pages 214 to 220 of the literature “Properties of Polymers 3rd, ELSEVIER , (1990)”. It refers to the obtained ⁇ p, and is calculated according to the description in the above column of the above document.
- the matrix resin is a resin exhibiting a certain hydrophobicity
- the water content of the wavelength selective absorption filter of the present invention can be set to a low water content such as 0.5% or less, and the wavelength selection of the present invention can be achieved. It is preferable from the viewpoint of improving the light resistance of the absorption filter.
- the resin may contain any conventional component in addition to the polymer.
- the fd of the matrix resin is a calculated value for the polymer constituting the matrix resin.
- the matrix resin include polystyrene resin and cyclic polyolefin resin from the viewpoint that the association inhibitor functions more effectively, and polystyrene resin is more preferable.
- the fd value of the polystyrene resin is 0.45 to 0.60
- the fd value of the cyclic polyolefin resin is 0.45 to 0.70.
- a resin component that imparts functionality to the wavelength selective absorption filter such as an extensible resin component and a peelability control resin component described later.
- the matrix resin is used in the sense that it contains an extensible resin component and a peelability control resin component in addition to the above-mentioned resin. It is preferable that the matrix resin contains a polystyrene resin from the viewpoint of sharpening the absorption waveform of the dye.
- the polystyrene contained in the polystyrene resin means a polymer containing a styrene component. Polystyrene preferably contains 50% by mass or more of the styrene component.
- the wavelength selective absorption filter of the present invention may contain one type of polystyrene or two or more types of polystyrene.
- the styrene component is a structural unit derived from a monomer having a styrene skeleton in its structure.
- Polystyrene preferably contains 70% by mass or more of a styrene component, and more preferably 85% by mass or more, from the viewpoint of controlling the photoelastic coefficient and hygroscopicity to values in a preferable range as a wavelength selective absorption filter. It is also preferable that polystyrene is composed of only a styrene component.
- examples of polystyrene composed of only a styrene component include homopolymers of styrene compounds and copolymers of two or more kinds of styrene compounds.
- the styrene compound is a compound having a styrene skeleton in its structure, and is a compound in which a substituent is introduced to the extent that the ethylenically unsaturated bond of styrene can act as a reactive (polymerizable) group in addition to styrene.
- styrene compounds include, for example, styrene; ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, and the like.
- Alkyl styrene such as p-ethyl styrene and tert-butyl styrene; hydroxyl group, alkoxy group, carboxy group and benzene nucleus of styrene such as hydroxy styrene, tert-butoxy styrene, vinyl benzoic acid, o-chloro styrene and p-chloro styrene. Examples thereof include substituted styrene in which a halogen atom or the like is introduced. Above all, from the viewpoint of availability, material price and the like, the polystyrene is preferably a homopolymer of styrene (that is, polystyrene).
- polystyrene may be a styrene-diene copolymer, a styrene-polymerizable unsaturated carboxylic acid ester copolymer, or the like.
- a mixture of polystyrene and synthetic rubber eg, polybutadiene and polyisoprene
- HIPS Impact-resistant polystyrene
- a rubber-like elastic body is dispersed in a continuous phase of a polymer containing a styrene component (for example, a copolymer of a styrene component and a (meth) acrylic acid ester component), and the above-mentioned copolymer is dispersed in the above-mentioned rubber-like elastic body.
- a styrene component for example, a copolymer of a styrene component and a (meth) acrylic acid ester component
- graft HIPS graft type impact resistant polystyrene
- so-called styrene-based elastomers can also be preferably used.
- the polystyrene may be hydrogenated (hydrogenated polystyrene may be used).
- the hydrogenated polystyrene is not particularly limited, but is a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) obtained by hydrogenating a styrene-butadiene-styrene block copolymer (SBS), and styrene-isoprene-styrene.
- SEBS hydrogenated styrene-butadiene-styrene block copolymer
- SEPS hydrogenated styrene-isoprene-styrene block copolymer
- SIS block copolymer
- As the hydrogenated polystyrene only one kind may be used, or two or more kinds may be used.
- polystyrene may be modified polystyrene.
- the modified polystyrene is not particularly limited, and examples thereof include polystyrene having a reactive group such as a polar group introduced therein, and specific examples thereof include acid-modified polystyrene such as maleic acid-modified and epoxy-modified polystyrene.
- polystyrene a plurality of types having different compositions, molecular weights, etc. can be used in combination.
- the polystyrene-based resin can be obtained by a conventional method such as an anion, lump, suspension, emulsification or solution polymerization method.
- at least a part of the unsaturated double bond of the benzene ring of the conjugated diene and the styrene monomer may be hydrogenated.
- the hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).
- polystyrene resin for example, "Clearlen 530L” and “Clearlen 730L” manufactured by Denki Kagaku Kogyo Co., Ltd., “Toughpren 126S” and “Asaplen T411” manufactured by Asahi Kasei Corporation, Clayton Polymer Japan. "Clayton D1102A”, “Clayton D1116A” manufactured by Stylolution Co., Ltd., “Stylolux S”, “Stylolux T” manufactured by Stylollution Co., Ltd., "Asaflex 840", “Asaflex 860” manufactured by Asahi Kasei Chemicals Co., Ltd.
- hydrogenated polystyrene resins examples include “Tough Tech H Series” manufactured by Asahi Kasei Chemicals Co., Ltd., “Kuraray G Series” (above, SEBS) manufactured by Shell Japan Co., Ltd., and “Dynaron” (hydrogenated) manufactured by JSR Co., Ltd. Styrene-butadiene random copolymer), “Septon” (SEPS) manufactured by Kuraray Co., Ltd., and the like.
- modified polystyrene resin examples include "Tough Tech M Series” manufactured by Asahi Kasei Chemicals Co., Ltd., “Epofriend” manufactured by Daicel Co., Ltd., “Polar Group Modified Dynaron” manufactured by JSR Co., Ltd., and Toagosei Co., Ltd. Examples include “Rezeda” made by.
- the wavelength selective absorption filter of the present invention preferably contains a polyphenylene ether resin in addition to the polystyrene resin.
- a polyphenylene ether resin By containing the polystyrene resin and the polyphenylene ether resin together, the toughness of the wavelength selective absorption filter can be improved, and the occurrence of defects such as cracks can be suppressed even in a harsh environment such as high temperature and high humidity.
- the polyphenylene ether resin Zylon S201A, 202A, S203A (all trade names) manufactured by Asahi Kasei Corporation can be preferably used. Further, a resin in which a polystyrene resin and a polyphenylene ether resin are mixed in advance may be used.
- the mixed resin of the polystyrene resin and the polyphenylene ether resin for example, Zylon 1002H, 1000H, 600H, 500H, 400H, 300H, 200H (all trade names) manufactured by Asahi Kasei Corporation are preferable. Can be used.
- the mass ratio of the two is preferably 99/1 to 50/50, preferably 98/2 to 60, for the polystyrene resin / polyphenylene ether resin. / 40 is more preferable, and 95/5 to 70/30 is even more preferable.
- the cyclic olefin compound that forms the cyclic polyolefin contained in the cyclic polyolefin resin is not particularly limited as long as it is a compound having a ring structure containing a carbon-carbon double bond, and is, for example, a monocyclic ring other than the norbornene compound and the norbornene compound. Cyclic olefin compound, cyclic conjugated diene compound, vinyl alicyclic hydrocarbon compound and the like can be mentioned.
- cyclic polyolefin examples include (1) a polymer containing a structural unit derived from a norbornene compound, (2) a polymer containing a structural unit derived from a monocyclic cyclic olefin compound other than the norbornene compound, and (3) a cyclic polymer.
- the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic cyclic olefin compound include a ring-opening polymer of each compound.
- the cyclic polyolefin is not particularly limited, but a polymer having a structural unit derived from a norbornene compound represented by the following general formula (A-II) or (A-III) is preferable.
- the polymer having the structural unit represented by the following general formula (A-II) is an addition polymer of the norbornene compound, and the polymer having the structural unit represented by the following general formula (A-III) is the norbornene compound. It is a ring-opening polymer.
- m is an integer of 0 to 4, preferably 0 or 1.
- R 3 to R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- the hydrocarbon group in the general formulas (AI) to (A-III) is not particularly limited as long as it is a group consisting of a carbon atom and a hydrogen atom, and is an alkyl group, an alkenyl group, an alkynyl group and an aryl group (aromatic hydrocarbon). Hydrogen group) and the like. Of these, an alkyl group or an aryl group is preferable.
- X2 and X3, Y2 and Y3 are independently hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, halogen atom and halogen atom, respectively.
- R 11 to R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- Z represents a hydrogen group or a hydrocarbon group substituted with a halogen
- W represents Si ( R 16 ) p D (3-p)
- R 16 indicates a hydrocarbon group having 1 to 10 carbon atoms
- D is a halogen atom
- -OCOR 17 or -OR 17 R 17 is a hydrogen atom having 1 to 10 carbon atoms.
- P is an integer of 0 to 3
- n is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6.
- R 3 to R 6 are preferably hydrogen atoms or -CH 3 , respectively, and more preferably hydrogen atoms in terms of moisture permeability.
- X 2 and X 3 a hydrogen atom, -CH 3 or -C 2 H 5 , is preferable, respectively, and a hydrogen atom is more preferable in terms of moisture permeability.
- Y 2 and Y 3 hydrogen atom, halogen atom (particularly chlorine atom) or-(CH 2 ) n COOR 11 (particularly -COOCH 3 ) are preferable, respectively, and hydrogen atom is more preferable in terms of moisture permeability.
- Other groups are appropriately selected.
- the polymer having a structural unit represented by the general formula (A-II) or (A-III) may further contain at least one structural unit represented by the following general formula (AI).
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- X 1 and Y 1 independently represent a hydrogen atom and carbon, respectively.
- R 11 to R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- Z represents a hydrogen group or a hydrocarbon group substituted with a halogen
- W represents Si ( R 16 ) p D (3-p) (R 16 indicates a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR 17 or -OR 17 (R 17 is a hydrogen atom having 1 to 10 carbon atoms). The group) is shown.
- P is an integer of 0 to 3).
- n is an integer from 0 to 10.
- the cyclic polyolefin having a structural unit represented by the general formula (A-II) or (A-III) has a structural unit derived from the above-mentioned norbornene compound with respect to the total mass of the cyclic polyolefin. It is preferably contained in an amount of 90% by mass or less, more preferably 30 to 85% by mass, further preferably 50 to 79% by mass, and most preferably 60 to 75% by mass.
- the ratio of the structural unit derived from the norbornene compound represents the average value in the cyclic polyolefin.
- Addition (co) polymers of norbornene compounds are described in JP-A No. 10-7732, JP-A-2002-504184, US Publication No. 2004/229157A1, International Publication No. 2004/070463, and the like. There is.
- the polymer of the norbornene compound is obtained by addition polymerization of the norbornene compounds (for example, a polycyclic unsaturated compound of norbornene).
- the norbornene compound if necessary, the norbornene compound, olefins such as ethylene, propylene and butene, conjugated diene such as butadiene and isoprene, non-conjugated diene such as ethylidene norbornene, and acrylonitrile, acrylic acid, and meta.
- olefins such as ethylene, propylene and butene
- conjugated diene such as butadiene and isoprene
- non-conjugated diene such as ethylidene norbornene
- acrylonitrile acrylic acid, and meta.
- examples thereof include a copolymer obtained by addition-copolymerizing with an ethylenically unsaturated compound such as acrylic acid, maleic anhydride, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate and vinyl chloride.
- Such an addition (co) polymer of norbornene compound is marketed by Mitsui Chemicals, Inc. under the trade name of Apel, and has different glass transition temperatures (Tg), APL8008T (Tg70 ° C) and APL6011T (Tg105 ° C). , APL6013T (Tg125 ° C.), APL6015T (Tg145 ° C.) and the like.
- pellets such as TOPAS 8007, 6013, and 6015 are commercially available from Polyplastics.
- the Appear 3000 is commercially available from Ferrania.
- polymer of the norbornene compound a commercially available product can be used.
- it is marketed by JSR under the trade name of Arton G or Arton F, and by Zeon Corporation under the trade names of Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280. There is.
- the hydride of the polymer of the norbornene compound can be synthesized by adding hydrogen after addition polymerization or metathesis ring-opening polymerization of the norbornene compound or the like.
- Examples of the synthesis method include JP-A No. 1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-159767, JP-A-2004-309979 and the like. It is described in each publication of.
- the molecular weight of the cyclic polyolefin is appropriately selected according to the purpose of use, but is equivalent to polyisoprene or polystyrene measured by a gel permeation chromatograph method of a cyclohexane solution (toluene solution if the polymer polymer is not dissolved).
- Mass average molecular weight is preferably in the range of 5000 to 500,000, preferably 8,000 to 200,000, and more preferably 10,000 to 100,000.
- a polymer having a molecular weight in the above range can achieve both mechanical strength of a molded product and moldability at a high level in a well-balanced manner.
- the wavelength selective absorption filter of the present invention preferably contains the matrix resin in an amount of 5% by mass or more, more preferably 20% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. preferable.
- the content of the matrix resin in the wavelength selective absorption filter of the present invention is usually 99.90% by mass or less, preferably 99.85% by mass or less.
- the cyclic polyolefin contained in the wavelength selective absorption filter of the present invention may be two or more kinds, or polymers having different composition ratios and molecular weights at least one may be used in combination. In this case, the total content of each polymer is within the above range.
- the wavelength selective absorption filter of the present invention can appropriately select and contain a component exhibiting extensibility (also referred to as an extensibility resin component) as a resin component.
- a component exhibiting extensibility also referred to as an extensibility resin component
- specific examples thereof include acrylonitrile-butadiene-styrene resin (ABS resin), styrene-butadiene resin (SB resin), isoprene resin, butadiene resin, polyether-urethane resin, and silicone resin. Further, these resins may be further hydrogenated as appropriate.
- ABS resin or SB resin As the extensible resin component, it is preferable to use ABS resin or SB resin, and it is more preferable to use SB resin.
- SB resin for example, a commercially available one can be used.
- commercial products TR2000, TR2003, TR2250 (above, trade name, manufactured by JSR Co., Ltd.), Clearen 210M, 220M, 730V (above, trade name, manufactured by Denka Co., Ltd.), Asaflex 800S, 805, 810, 825, 830, 840 (above, trade name, manufactured by Asahi Kasei Corporation), Epolex SB2400, SB2610, SB2710 (above, trade name, Sumitomo Chemical Co., Ltd.) and the like can be mentioned.
- the extensible resin component As the extensible resin component, a sample having a thickness of 30 ⁇ m and a width of 10 mm was prepared by using the extensible resin component alone, and the fracture elongation at 25 ° C. was measured based on JIS 7127. Those having an elongation of 10% or more are preferable, and those having an elongation of 20% or more are more preferable.
- the wavelength selective absorption filter of the present invention is peeled off as a resin component when it is manufactured by a method including a step of peeling the wavelength selective absorption filter from the release film among the methods for manufacturing the wavelength selective absorption filter of the present invention described later. It is preferable because it can contain a component that controls the property (peeling property control resin component).
- peelability of the wavelength selective absorption filter from the release film it is possible to prevent the wavelength selective absorption filter from having peeled marks after peeling, and it is possible to cope with various processing speeds in the peeling process. Is possible. As a result, it is possible to obtain a favorable effect on improving the quality and productivity of the wavelength selective absorption filter.
- the peelability control resin component is not particularly limited and can be appropriately selected depending on the type of the release film.
- a polyester resin also referred to as a polyester additive
- a cellulose polymer film is used as the release film.
- a polyester-based elastomer is suitable.
- a polyester-based polymer film is used as the release film, for example, a styrene-based elastomer is also preferably used as the release control resin component.
- the polyester-based additive can be obtained by a conventional method such as a dehydration condensation reaction between a polyhydric basic acid and a polyhydric alcohol, an addition of an anhydrous dibasic acid to the polyhydric alcohol, and a dehydration condensation reaction.
- a polycondensation ester formed from an acid and a diol is preferred.
- the mass average molecular weight (Mw) of the polyester-based additive is preferably 500 to 50,000, more preferably 750 to 40,000, and even more preferably 2,000 to 30,000.
- the mass average molecular weight of the polyester-based additive is at least the above-mentioned preferable lower limit value, it is preferable from the viewpoint of brittleness and moist heat durability, and when it is at least the above-mentioned preferable upper limit value, it is preferable from the viewpoint of compatibility with the resin.
- the mass average molecular weight of the polyester-based additive is a value of the mass average molecular weight (Mw) in terms of standard polystyrene measured under the following conditions.
- Mn is a number average molecular weight in terms of standard polystyrene.
- GPC Gel permeation chromatograph device (HLC-8220GPC manufactured by Tosoh Corporation, Column: Guard columns HXL-H, TSK gel G7000HXL, TSK gel GMHXL 2 and TSK gel G2000HXL manufactured by Tosoh Corporation are connected in sequence.
- dicarboxylic acid can be preferably mentioned.
- dicarboxylic acid include an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and an aromatic dicarboxylic acid or a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid can be preferably used.
- aromatic dicarboxylic acids aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable, and aromatic dicarboxylic acids having 8 to 14 carbon atoms are more preferable.
- aromatic dicarboxylic acids having 8 to 14 carbon atoms are more preferable.
- at least one of phthalic acid, isophthalic acid and terephthalic acid is preferably mentioned.
- an aliphatic dicarboxylic acid having 3 to 8 carbon atoms is preferable, and an aliphatic dicarboxylic acid having 4 to 6 carbon atoms is more preferable.
- at least one of succinic acid, maleic acid, adipic acid and glutaric acid is preferably mentioned, and at least one of succinic acid and adipic acid is more preferable.
- diol component constituting the polyester-based additive examples include aliphatic diols and aromatic diols, and aliphatic diols are preferable.
- aliphatic diols examples include an aliphatic diol having 2 to 4 carbon atoms, and an aliphatic diol having 2 to 3 carbon atoms is more preferable.
- the aliphatic diol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol and 1,4-butylene glycol, which are used alone. Alternatively, two or more types can be used in combination.
- the polyester-based additive is particularly preferably a compound obtained by condensing at least one of phthalic acid, isophthalic acid and terephthalic acid with an aliphatic diol.
- the end of the polyester-based additive may be sealed by reacting with a monocarboxylic acid.
- a monocarboxylic acid used for encapsulation, an aliphatic monocarboxylic acid is preferable, acetic acid, propionic acid, butanoic acid, benzoic acid and derivatives thereof are preferable, acetic acid or propionic acid is more preferable, and acetic acid is further preferable.
- polyester-based additives examples include ester-based resin polyesters manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (for example, LP050, TP290, LP035, LP033, TP217, TP220) and ester-based resin Byron manufactured by Toyobo Co., Ltd. (for example, Byron 245). , Byron GK890, Byron 103, Byron 200, Byron 550. GK880) and the like.
- the polystyrene-based elastomer is not particularly limited and can be appropriately selected according to the purpose.
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- SEP polystyrene-poly (ethylene).
- SEPS Polystyrene-Poly (SIS hydrogenated type), Polystyrene-Poly (ethylene-butylene) -Polystyrene triblock copolymer (SEBS) (SBS hydrogenated type), Polystyrene-Poly Examples thereof include (ethylene-ethylene-propylene) -polystyrene triblock copolymer (SEEPS), polystyrene-poly (ethylene-propylene) diblock copolymer, and polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer.
- polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymers or polystyrene-poly (ethylene-ethylene-propylene) -polystyrene triblock copolymers are preferred.
- the content of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably 90% by mass or less, more preferably 55% by mass or less, further preferably 48% by mass or less, further preferably 35% by mass or less, and 33% by mass or less. Even more preferable.
- the lower limit of the ratio of the repeating unit derived from styrene may be more than 0% by mass and may be 10% by mass or more.
- the polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer having a styrene block at one end or both ends, and a styrene block at both ends. Is even more preferred.
- styrene blocks peating units derived from styrene
- the heat resistance tends to be further improved. This is due to the presence of highly heat resistant styrene-derived repeating units at the ends.
- the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, it tends to be more excellent in heat resistance, which is more preferable from the viewpoint of solubility in a solvent.
- the polystyrene-based elastomer is a hydrogenated additive, its stability against heat is improved, and deterioration such as decomposition or polymerization is unlikely to occur. Further, it is more preferable from the viewpoint of solubility in a solvent.
- the unsaturated double bond amount of the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and less than 0.5 mmol per 1 g of the polystyrene-based elastomer. More preferred.
- the amount of unsaturated double bond referred to here does not include the amount of unsaturated double bond in the benzene ring derived from styrene.
- the unsaturated double bond amount can be calculated by NMR (nuclear magnetic resonance) measurement.
- the "styrene-derived repeating unit” is a styrene-derived structural unit contained in the polymer when styrene or a styrene derivative is polymerized, and may have a substituent.
- the styrene derivative include ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like.
- the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an acetoxy group, a carboxyl group and the like.
- polystyrene-based elastomer for example, the polystyrene-based elastomer described in paragraph 0027 of JP-A-2018-355279 can be used.
- the content of the peelability control resin component in the wavelength selective absorption filter of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more in the matrix resin.
- the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. From the viewpoint of obtaining appropriate adhesion, the above-mentioned preferable range is preferable.
- the wavelength selection filter of the present invention contains a compound having a polar group (also referred to as an “association inhibitor” in the present invention).
- the association inhibitor interacts with the above dye to suppress or prevent the association of dye molecules in the wavelength selective absorption filter of the present invention, and the absorption waveform of the dye A or D contained in the wavelength selective absorption filter. It is a compound that expresses the function of sharpening and improving the light resistance. Unlike the dyes described above, the association inhibitor is a compound that does not substantially exhibit color when contained in the wavelength selective absorption filter of the present invention. Further, the association inhibitor is a compound that exhibits a function of suppressing the association of dye molecules with respect to the dye A or D dispersed or dissolved in the resin in the wavelength selective absorption filter of the present invention, and is described above. Different from resin.
- the molecular weight of the association inhibitor is 1000 or less, preferably 100 to 1000, more preferably 200 to 1000, and even more preferably 200 to 900.
- the association inhibitor is not a compound exhibiting a function as an anti-fading agent described later.
- the association inhibitor preferably does not have a fluorinated alkyl group from the viewpoint of uniform dispersion in the filter.
- the association inhibitor may have at least one of a carboxylic acid ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a urethane bond and a sulfonyl bond, and may have two or more of them. good.
- the upper limit of the total number of polar groups is not particularly limited, but for example, 10 or less is preferable, and 6 or less is more preferable.
- the type of the polar group contained in the association inhibitor is not particularly limited and may be one type or two or more types, but it is preferably one type or two types, and one type is preferable. It is more preferable to have.
- the types of polar groups include one type of polar group classified as a carboxylic acid ester bond, one type of polar group classified as a carboxylic acid amide bond, and one type of polar group classified as a sulfonic acid amide bond.
- a polar group classified as a urethane bond is counted as one type, and a polar group classified as a sulfonyl bond is counted as one type.
- the association inhibitor preferably has a carboxylic acid ester bond or a carboxylic acid amide bond.
- association inhibitor a compound represented by any of the following general formulas (2) to (14) and (18) is preferable.
- the compound has two or more polar groups among the carboxylic acid ester bond, the carboxylic acid amide bond, the sulfonic acid amide bond, the urethane bond and the sulfonyl bond, it is based on the polar group having the highest priority of the compound. It shall be classified into each formula.
- the order of priority of the polar groups here is carboxylic acid amide bond> carboxylic acid ester bond> sulfonic acid amide bond> sulfonyl bond> urethane bond in descending order of priority.
- the compound represented by the following general formula (2) or (3) is a compound having a structure in which at least one of a carboxylic acid ester bond or a carboxylic acid amide bond is directly bonded to a ring structure. However, if it also corresponds to the compound represented by the general formula (18), it is classified into the compound represented by the general formula (18).
- the compound represented by any of the general formulas (4) to (12) described later is a compound having at least one of a carboxylic acid ester bond, a carboxylic acid amide bond, and a urethane bond.
- the compound represented by the general formula (13) described later is a compound having a sulfonic acid amide bond.
- the compound represented by the general formula (14) described later is a compound having a sulfonyl bond.
- the compound represented by the general formula (18) described later is a compound having a carboxylic acid amide bond.
- Z represents a carbon atom, an oxygen atom, a sulfur atom or> NR 25
- R 25 represents a hydrogen atom or an alkyl group
- Y 21 and Y 22 represent an acyloxy group, an alkoxycarbonyl group, an amide group or a carbamoyl group.
- m is an integer of 1 to 5
- n is an integer of 1 to 6.
- a 5- or 6-membered ring having Z as a ring-constituting atom may have a substituent.
- a 5- or 6-membered ring having Z as a ring-constituting atom has a plurality of substituents, adjacent substituents may be bonded to each other to form a ring.
- the ring formed by bonding the adjacent substituents to each other may be an aromatic ring or a non-aromatic ring.
- Examples of the 5- or 6-membered ring having Z as a ring-constituting atom include tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, thiane, pyrrolidine, piperidine and the like.
- examples of this condensed ring structure include indoline, isoindoline, chroman, and isochroman.
- a cyclic ester or cyclic amide structure include lactones such as tetrahydro-2-furanone (also referred to as 5-pentanolide), tetrahydro-2-pyrone (also referred to as 6-hexanolide), and 4-butan lactam (also referred to as 6-hexanolide). Lactams such as 2-pyrrolidone) and 5-pentanlactam (also referred to as 2-piperidone) can be mentioned.
- R 25 represents a hydrogen atom or an alkyl group.
- the alkyl group that can be taken as R25 may be chain-shaped, branched or cyclic, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- Alkyl groups that can be taken as R25 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, and the like.
- Decyl dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, bicyclo [2.2.2] octane -3-Il can be mentioned.
- Y 21 and Y 22 represent an acyloxy group, an alkoxycarbonyl group, an amide group or a carbamoyl group.
- the acyloxy group that can be taken as Y 21 or Y 22 the number of carbon atoms is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- the number of carbon atoms is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- the number of carbon atoms is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- the number of carbon atoms is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- Lucarbamoyl n-hexylcarbamoyl, cyclohexylcarbamoyl, 2-ethylhexylcarbamoyl, 2-ethylbutylcarbamoyl, t-octylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, 1-adamantancarbamoyl, 2-adamantancarbamoyl, n-decylcarbamoyl , N-dodecylcarbamoyl, n-tetradecylcarbamoyl, n-hexadecylcarbamoyl and the like.
- adjacent Y 21s may be connected to each other to form a ring
- adjacent Y 22s may be connected to each other to form a ring
- Y 31 to Y 70 represent an acyloxy group, an alkoxycarbonyl group, an amide group, a carbamoyl group or a carbamoyloxy group
- V 31 to V 43 are hydrogen atoms or aliphatic groups.
- L 31 to L 64 and L 66 to L 80 represent divalent saturated linking groups having 0 to 40 atoms and 0 to 20 carbon atoms.
- the fact that the number of atoms of L 31 to L 64 and L 66 to L 80 is 0 means that the groups located at both ends of the linking groups represented by L 31 to L 64 and L 66 to L 80 are simple. It means that they are directly connected by binding.
- Y 31 to Y 70 represent an acyloxy group, an alkoxycarbonyl group, an amide group, a carbamoyl group or a carbamoyloxy group.
- the acyloxy group, alkoxycarbonyl group, amide group and carbamoyl group which can be taken as Y 31 to Y 70 include the acyloxy group, alkoxycarbonyl group and amide which can be taken as Y 21 or Y 22 in the above general formula (2) or (3).
- the description of the group and the carbamoyl group can be applied respectively.
- the description of the carbamoyl group that can be taken as Y 21 or Y 22 in the above general formula (2) or (3) can be applied.
- V 31 to V 43 represent a hydrogen atom or an aliphatic group.
- the number of carbon atoms of the aliphatic group that can be obtained as V 31 to V 43 is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.
- the aliphatic group is preferably an aliphatic hydrocarbon group, and may be chain-like, branched or cyclic. More preferably, it is an alkyl group, an alkenyl group or an alkynyl group.
- Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, decyl, dodecyl and eicosyl.
- alkenyl group examples include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexene-1-yl and the like, and examples of the alkynyl group include ethynyl and the like.
- Propargil can be mentioned.
- L 31 to L 64 and L 66 to L 80 represent divalent saturated linking groups having 0 to 40 atoms and 0 to 20 carbon atoms.
- the fact that the number of atoms of L 31 to L 64 and L 66 to L 80 is 0 means that the groups located at both ends of the linking groups represented by L 31 to L 80 are directly bonded by a single bond. Means that you are.
- Preferred examples of the divalent saturated linking groups that can be taken as L 31 to L 64 and L 66 to L 80 include alkylene groups (eg, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc.
- Two or more of these divalent groups may be bonded to each other to form a divalent complex group, and examples of the composite substituent include-(CH 2 ) 2 O (CH 2 ) 2 -,-. (CH 2 ) 2 O (CH 2 ) 2 O (CH 2 )-,-(CH 2 ) 2 S (CH 2 ) 2- or-(CH 2 ) 2 O 2 C (CH 2 ) 2- be able to.
- Preferred examples of the compound represented by any of the general formulas (4) to (12) include citrate esters (eg, triethyl O-acetylcitrate, tributyl O-acetylcitrate, acetyltriethyl citrate, citrate).
- citrate esters eg, triethyl O-acetylcitrate, tributyl O-acetylcitrate, acetyltriethyl citrate, citrate.
- oleic acid ester eg, ethyl oleate, butyl oleate, 2-eth
- Citric acid esters and pyrrolidone carboxylic acid esters described in the publication (2-pyrrolidone-5-carboxylate methyl, 2-pyrrolidone-5-carboxylate ethyl, 2-pyrrolidone-5-carboxylate butyl, 2-pyrrolidone-5 -Carboxylic acid 2-ethylhexyl), cyclohexanedicarboxylic acid ester (cis-1,2-cyclohexanedicarboxylate dibutyl, trans-1,2-cyclohexanedicarboxylate dibutyl, cis-1,4-cyclohexanedicarboxylate dibutyl, trans-1, Dibutyl 4-cyclohexanedicarboxylate, etc.), xylitol carboxylate ester (xylitol pentaacetate, xylitol tetraacetate, xylitol pentapropionate, etc.) and the like
- R 1 represents an alkyl group or an aryl group
- R 2 and R 3 represent a hydrogen atom, an alkyl group or an aryl group.
- the total number of carbon atoms of R 1 , R 2 and R 3 is 10 or more.
- R 4 and R 5 represent an alkyl group or an aryl group.
- the total number of carbon atoms of R 4 and R 5 is 10 or more.
- the alkyl group that can be taken as R 1 to R 5 may be linear, branched, or cyclic, and the number of carbon atoms is preferably 1 to 25, more preferably 6 to 25. 6 to 20 are more preferable.
- the number of carbon atoms of the aryl group that can be obtained as R 1 to R 5 is preferably 6 to 30, and more preferably 6 to 24.
- phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, triphenylphenyl can be mentioned.
- the alkyl group and aryl group that can be taken as R 1 to R 5 may have a substituent.
- the substituents that may have include a halogen atom (fluorine atom, chlorine atom, etc.), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, a sulfonyl group, and a sulfone.
- Preferred examples include an amide group, an amino group, a hydroxy group or a cyano group.
- a substituent formed by combining two or more of these substituents is also preferable.
- substituent which the alkyl group and the aryl group which can be taken as R 1 to R 5 may have, an alkyl group, an aryl group, an alkoxy group, a sulfone group or a sulfonamide group is more preferable.
- the total number of carbon atoms of R 1 to R 3 is 10 or more, preferably 10 to 40, and more preferably 12 to 30.
- the total number of carbon atoms of R 4 and R 5 is 10 or more, preferably 10 to 40, more preferably 12 to 30.
- R 1 represents an alkyl group or an aryl group.
- R 2 and R 3 represent a hydrogen atom, an alkyl group or an aryl group, and an alkyl group or an aryl group is preferable.
- the alkyl group that can be taken as R 1 to R 3 may be linear, branched, or cyclic, and has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and 1 to 12 carbon atoms. Is even more preferable.
- Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and a cyclohexyl group is particularly preferable.
- the aryl group that can be taken as R 1 to R 3 preferably has 6 to 36 carbon atoms, and more preferably 6 to 24 carbon atoms. Of these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
- the alkyl group and aryl group that can be taken as R 1 to R 3 may have a substituent, and the substituent includes a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkyl group, and the like.
- a halogen atom for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom
- Aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group, carbamoyl group or acylamino group are preferable, and more preferably halogen.
- It is an atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonylamino group, a carbamoyl group or an acylamino group, and more preferably an alkyl group, an aryl group, a sulfonylamino group or an acylamino group.
- the substituents that the alkyl group and the aryl group that can be taken as R 1 to R 3 may have may be further substituted with a substituent.
- the description of the above-mentioned alkyl group which can be taken as R 1 to R 3 and the substituent which may be possessed by the aryl group can be preferably applied, and for example, the alkyl group can be used. Can be mentioned.
- the compound represented by the general formula (18) preferably has a cyclic structure from the viewpoint of further improving the light resistance.
- the cyclic structure may be either a saturated or unsaturated aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and is preferably an aromatic hydrocarbon ring.
- the number of cyclic structures in the compound is not particularly limited, for example, 1 to 7 is preferable, 1 to 5 is more preferable, and 2 or 3 is further preferable.
- the compound represented by the general formula (18) does not have a long-chain alkyl group from the viewpoint of further improving the light resistance.
- the long-chain alkyl group means a group having 7 or more carbon atoms constituting the longest bond among the carbon-carbon bonds constituting the alkyl group.
- a compound having an alkoxycarbonyl group on the benzene ring is also preferably mentioned.
- the number of alkoxycarbonyl groups on the benzene ring is not particularly limited, preferably 1 to 3, and more preferably 2 or 3.
- the benzene ring may have a substituent other than the alkoxycarbonyl group, and examples thereof include a sulfamoyl group and a sulfonyl group.
- the sulfamoyl group preferably has 0 to 20 carbon atoms, more preferably 0 to 12, further preferably 0 to 6, and the sulfonyl group preferably has 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms.
- These sulfamoyl groups and sulfonyl groups may be further substituted with a substituent, and examples thereof include an alkoxycarbonyl group and an acyloxy group.
- a substituent examples thereof include an alkoxycarbonyl group and an acyloxy group.
- a phthalate ester compound or a trimellitic acid ester compound is preferable.
- the phthalate ester compound an ester compound of phthalic acid (any isomer of ortho, meta, or para) and an alcohol having 4 to 10 carbon atoms is preferable. Specific examples thereof include dicyclohexyl phthalate, diphenyl phthalate, and ditrill phthalate.
- trimellitic acid ester compound an ester compound of trimellitic acid and an alcohol having 4 to 10 carbon atoms is preferable.
- Specific examples thereof include tributyltrimellitic acid, tri (2-ethylhexyl) trimellitic acid, trinormaloctyltrimellitic acid, trinormaldecyltrimellitic acid, and triisodecyltrimellitic acid.
- tributyl trimellitic acid, tri (2-ethylhexyl) trimellitic acid, or triisodecyl trimellitic acid is preferable.
- the content of the association inhibitor in the wavelength selective absorption filter of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass.
- the association inhibitor is preferably contained in the wavelength selective absorption filter of the present invention in a proportion of 10 to 1000 parts by mass, preferably 30 to 700 parts by mass, based on 100 parts by mass of the total content of the dye A and the dye C. It is more preferably contained in a proportion of parts, and further preferably contained in a proportion of 50 to 500 parts by mass.
- the wavelength selective absorption filter of the present invention may contain a dye fading inhibitor, a matting agent, a leveling (surfactant) agent, and the like, in addition to the above-mentioned dye, matrix resin, and association inhibitor.
- the wavelength selective absorption filter of the present invention may contain a dye fading inhibitor (simply also referred to as an antifading agent) in order to prevent the fading of the dye containing at least one of the dyes A and D.
- a dye fading inhibitor (simply also referred to as an antifading agent) in order to prevent the fading of the dye containing at least one of the dyes A and D.
- the anti-fading agent include the antioxidants described in paragraphs [0143] to [0165] of International Publication No. 2015/005398, the radical scavengers described in the same [0166] to [0199], and the same [0205].
- -A commonly used anti-fading agent such as the deterioration-preventing agent described in [0206] can be used without particular limitation.
- the content of the anti-fading agent in the wavelength selective absorption filter of the present invention is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, based on 100% by mass of the total mass of the wavelength selective absorption filter. be.
- a leveling agent can be appropriately mixed with the wavelength selective absorption filter of the present invention.
- the leveling agent a commonly used compound can be used, and a fluorine-containing surfactant is particularly preferable.
- the compounds described in paragraph numbers [0028] to [0056] in the specification of JP-A-2001-330725 can be mentioned.
- the content of the leveling agent in the wavelength selective absorption filter of the present invention is appropriately adjusted according to the purpose.
- the wavelength selective absorption filter of the present invention includes a low molecular weight plasticizer, an oligomer plasticizer, a retardation adjuster, an ultraviolet absorber, an antioxidant, a peeling accelerator, an infrared absorber, an antioxidant, and a filler. And may contain a compatibilizer and the like.
- the wavelength selective absorption filter of the present invention is produced by a solution film forming method, a melt extrusion method, or a method of forming a coating layer on a base film (release film) by an arbitrary method (coating method) by a conventional method. It can be combined with stretching as appropriate.
- the solution film forming method and the melt extrusion method the solution film forming method and the melt extrusion method described in [0259] to [0265] of International Publication No. 2019/189463 can be used without particular limitation.
- the "filter of the present invention” or “filter” in International Publication No. 2019/189463 shall be read as the wavelength selective absorption filter of the present invention.
- the wavelength selective absorption filter of the present invention is preferably produced by a coating method.
- a solution of the material of the wavelength selective absorption filter of the present invention is appropriately subjected to a concentration step, a filtration step, or the like, and then applied onto a release film and dried to form a coating layer.
- a mold release agent or the like may be appropriately applied to the surface of the release film in advance in order to control the adhesiveness with the coating layer.
- the coating layer can be used by laminating it with another member via an adhesive layer in a later step and then peeling off the release film. Any adhesive can be appropriately used as the adhesive constituting the adhesive layer.
- the release film can be appropriately stretched together with the release film coated with the solution of the material of the wavelength selective absorption filter of the present invention or the coating layer is laminated.
- the solvent used for the solution of the wavelength selective absorption filter material is that the wavelength selective absorption filter material can be dissolved or dispersed, that it tends to have a uniform surface shape in the coating process and the drying process, that the liquid storage stability can be ensured, and that it is appropriate. It can be appropriately selected from the viewpoint of having a saturated vapor pressure and the like.
- the timing at which the dye and the association inhibitor are added to the wavelength selective absorption filter material is not particularly limited as long as they are added at the time of film formation. For example, it may be added at the time of synthesizing the matrix resin, or may be mixed with the wavelength selective absorption filter material at the time of preparing the coating liquid of the wavelength selective absorption filter material. The same applies to other components that may be contained in the wavelength selective absorption filter such as a leveling agent.
- the release film used for forming the wavelength selective absorption filter by a coating method or the like preferably has a film thickness of 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m, and even more preferably 15 to 55 ⁇ m.
- the film thickness is at least the above-mentioned preferable lower limit value, it is easy to secure sufficient mechanical strength, and failures such as curl, wrinkles, and buckling are unlikely to occur.
- the film thickness is not more than the above preferable upper limit value, the surface pressure applied to the multilayer film when the multilayer film of the wavelength selective absorption filter and the release film of the present invention is stored, for example, in the form of a long roll. Is easy to adjust to an appropriate range, and adhesion failure is unlikely to occur.
- the surface energy of the release film is not particularly limited, but is the relationship between the surface energy of the material and coating solution of the wavelength selective absorption filter and the surface energy of the surface on the side forming the wavelength selective absorption filter of the release film.
- the surface energy of the release film can be calculated from the contact angle values of water and methylene iodide using the Owens method.
- DM901 contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
- the surface energy of the release film on the side where the wavelength selective absorption filter is formed is preferably 41.0 to 48.0 mN / m, and more preferably 42.0 to 48.0 mN / m.
- the surface energy is at least the above-mentioned preferable lower limit value, the uniformity of the thickness of the wavelength selective absorption filter is enhanced, and when it is at least the above-mentioned preferable upper limit value, the peeling force of the wavelength selective absorption filter from the release film is within an appropriate range. Easy to control.
- the surface unevenness of the release film is not particularly limited, but the surface energy, hardness, and surface unevenness of the surface of the wavelength selective absorption filter and the surface opposite to the side on which the wavelength selective absorption filter of the release film is formed are opposite.
- it may be adjusted for the purpose of preventing adhesion failure when the multi-layer film of the wavelength selective absorption filter of the present invention and the release film is stored in a long roll form. can.
- Increasing the surface unevenness tends to suppress adhesion failure, and reducing the surface unevenness tends to reduce the surface unevenness of the wavelength selective absorption filter and reduce the haze of the wavelength selective absorption filter. be able to.
- any material and film can be appropriately used as such a release film.
- Specific examples thereof include polyester polymers (including polyethylene terephthalate films), olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulosic polymers, polyamide polymers and the like.
- surface treatment can be appropriately performed. For example, corona treatment, room temperature plasma treatment, saponification treatment and the like can be performed to reduce the surface energy, and silicone treatment, fluorine treatment, olefin treatment and the like can be performed to increase the surface energy.
- the peeling force between the wavelength selective absorption filter and the release film is the internal strain of the wavelength selective absorption filter material, the release film material, and the wavelength selective absorption filter. Etc. can be adjusted and controlled.
- This peeling force can be measured, for example, in a test of peeling the peeling film in the 90 ° direction, and the peeling force when measured at a speed of 300 mm / min is preferably 0.001 to 5N / 25 mm, preferably 0.01. ⁇ 3N / 25mm is more preferable, and 0.05 to 1N / 25mm is even more preferable.
- peeling of the release film other than the peeling step can be prevented, and if it is at least the above preferable upper limit value, peeling failure in the peeling step (for example, zipping and cracking of the wavelength selective absorption filter). Can be prevented.
- the film thickness of the wavelength selective absorption filter of the present invention is not particularly limited, but is preferably 1 to 18 ⁇ m, more preferably 1 to 12 ⁇ m, still more preferably 1 to 8 ⁇ m.
- it is not more than the above preferable upper limit value it is possible to suppress the decrease in the degree of polarization due to the fluorescence emitted by the dye (dye) by adding the dye to the thin film at a high concentration.
- the effects of the quencher and the anti-fading agent are likely to be exhibited.
- it is at least the above-mentioned preferable lower limit value it becomes easy to maintain the uniformity of the absorbance in the plane.
- the film thickness of 1 to 18 ⁇ m means that the thickness of the wavelength selective absorption filter is within the range of 1 to 18 ⁇ m regardless of the location. This also applies to the film thickness of 1 to 12 ⁇ m and 1 to 8 ⁇ m.
- the film thickness can be measured with an electronic micrometer manufactured by Anritsu Corporation.
- the minimum transmittance of the wavelength selective absorption filter of the present invention at a wavelength of 390 to 440 nm is preferably 0% or more and 98% or less, more preferably 0% or more and 90% or less, and further preferably 0% or more and 80% or less. Further, the minimum transmittance of the wavelength selective absorption filter of the present invention at a wavelength of 480 to 520 nm is preferably 5% or more and 98% or less, more preferably 10% or more and 95% or less, and further preferably 20% or more and 90% or less.
- the minimum transmittance of the wavelength selective absorption filter of the present invention at a wavelength of 580 to 620 nm is preferably 0% or more and 99% or less, more preferably 0% or more and 98% or less, and further preferably 0% or more and 95% or less.
- the minimum transmittance of the wavelength selective absorption filter of the present invention at a wavelength of 680 to 780 nm is preferably 0% or more and 95% or less, more preferably 0% or more and 90% or less, and further preferably 0% or more and 80% or less.
- the wavelength selective absorption filter of the present invention having the transmittance adjusted to the above range into a display device (preferably a self-luminous display device), a display having higher brightness, more suppression of external light reflection, and a smaller color difference of reflected light. Performance is obtained.
- the transmittance of the wavelength selective absorption filter of the present invention can be adjusted by the type and addition amount of the dye, the type and addition amount of the association inhibitor, the resin type and the like.
- the wavelength selective absorption filter of the present invention may be subjected to a hydrophilization treatment by any glow discharge treatment, corona discharge treatment, alkali saponification treatment, or the like, and the corona discharge treatment is preferably used. It is also preferable to apply the method disclosed in Japanese Patent Application Laid-Open No. 6-94915, Japanese Patent Application Laid-Open No. 6-118232, and the like.
- the obtained membrane can be subjected to a heat treatment step, a superheated steam contact step, an organic solvent contact step, or the like, if necessary. Moreover, you may carry out surface treatment as appropriate.
- a pressure-sensitive adhesive composition in which a (meth) acrylic resin, a styrene-based resin, a silicone-based resin, or the like is used as a base polymer, and a cross-linking agent such as an isocyanate compound, an epoxy compound, or an aziridin compound is added thereto. It is also possible to apply a layer consisting of. Preferably, the description of the pressure-sensitive adhesive layer in the display device described later can be applied.
- the wavelength selective absorption filter of the present invention has a gas barrier layer directly arranged on at least one surface of the wavelength selective absorption filter of the present invention, and the gas barrier layer contains a crystalline resin, and the thickness of the layer is 0. It is preferably 1 ⁇ m to 10 ⁇ m and the oxygen permeability of the layer is 60 cc / m 2 ⁇ day ⁇ atm or less.
- the "crystalline resin” is a resin having a melting point that undergoes a phase transition from a crystal to a liquid when the temperature is raised, and can impart gas barrier properties related to oxygen gas to the gas barrier layer. Is.
- the wavelength selective absorption filter of the present invention has the gas barrier layer at least on the surface where the wavelength selective absorption filter of the present invention comes into contact with air when incorporated into the display device of the present invention, whereby the wavelength selective absorption of the present invention is present. It is possible to suppress a decrease in the absorption intensity of the dye in the filter and improve the light resistance. As long as the gas barrier layer is provided at the interface of the wavelength selective absorption filter of the present invention in contact with air, the gas barrier layer may be provided on only one side of the wavelength selective absorption filter, or may be provided on both sides.
- the crystalline resin contained in the gas barrier layer is a crystalline resin having a gas barrier property, and can be used without particular limitation as long as the desired oxygen permeability can be imparted to the gas barrier layer.
- the crystalline resin include polyvinyl alcohol and polyvinylidene chloride, and polyvinyl alcohol is preferable because the crystalline portion can effectively suppress the permeation of gas.
- the polyvinyl alcohol may or may not be modified.
- the modified polyvinyl alcohol include modified polyvinyl alcohol having a group such as an acetoacetyl group and a carboxyl group introduced therein.
- the saponification degree of the polyvinyl alcohol is preferably 80.0 mol% or more, more preferably 90.0 mol% or more, further preferably 97.0 mol% or more, and particularly preferably 98.0 mol% or more from the viewpoint of further enhancing the oxygen gas barrier property. preferable.
- the upper limit is not particularly limited, but 99.99 mol% or less is practical.
- the saponification degree of the polyvinyl alcohol is a value calculated based on the method described in JIS K 6726 1994.
- the gas barrier layer may contain any component usually contained in the gas barrier layer as long as the effect of the present invention is not impaired.
- the gas barrier layer may contain a solvent such as water and an organic solvent derived from the manufacturing process as long as the effect of the present invention is not impaired.
- the content of the crystalline resin in the gas barrier layer is, for example, preferably 90% by mass or more, more preferably 95% by mass or more, based on 100% by mass of the total mass of the gas barrier layer.
- the upper limit is not particularly limited, but may be 100% by mass.
- the oxygen permeability of the gas barrier layer is 60 cc / m 2 ⁇ day ⁇ atm or less, preferably 50 cc / m 2 ⁇ day ⁇ atm or less, and more preferably 30 cc / m 2 ⁇ day ⁇ atm or less. It is preferably 10 cc / m 2 ⁇ day ⁇ atm or less, more preferably 5 cc / m 2 ⁇ day ⁇ atm or less, and most preferably 1 cc / m 2 ⁇ day ⁇ atm or less.
- the practical lower limit is 0.001 cc / m 2 ⁇ day ⁇ atm or more, preferably more than 0.05 cc / m 2 ⁇ day ⁇ atm, for example.
- the oxygen permeability of the gas barrier layer is a value measured based on the gas permeability test method based on JIS K 7126-2 2006.
- an oxygen permeability measuring device manufactured by MOCON, OX-TRAN2 / 21 (trade name) can be used.
- the measurement conditions are a temperature of 25 ° C. and a relative humidity of 50%.
- the thickness of the gas barrier layer is preferably 0.5 ⁇ m to 5 ⁇ m, more preferably 1.0 ⁇ m to 4.0 ⁇ m, from the viewpoint of further improving the light resistance.
- the thickness of the gas barrier layer is measured by the method described in Examples described later.
- the crystallinity of the crystalline resin contained in the gas barrier layer is preferably 25% or more, more preferably 40% or more, still more preferably 45% or more.
- the upper limit is not particularly limited, but it is practically 55% or less, and preferably 50% or less.
- the crystallinity of the crystalline resin contained in the gas barrier layer is as follows. Apple. Pol. Sci. , 81, 762 (2001), and is a value measured and calculated by the following method. Using a DSC (Differential Scanning Calorimeter), the temperature of the sample peeled from the gas barrier layer is raised at 10 ° C./min over the range of 20 ° C. to 260 ° C., and the heat of fusion 1 is measured.
- the heat of fusion 1 and the heat of fusion 2 may be in the same unit, and are usually Jg -1 .
- the method for forming the gas barrier layer is not particularly limited, and examples thereof include a method for forming the gas barrier layer by a casting method such as spin coating and slit coating by a conventional method. Further, a method of attaching a commercially available resin gas barrier film or a resin gas barrier film prepared in advance to the wavelength selective absorption filter of the present invention can be mentioned.
- the wavelength selective absorption filter of the present invention may appropriately have any optical film as long as the effects of the present invention are not impaired.
- the above-mentioned optional optical film is not particularly limited in terms of optical properties and materials, but is a film containing (or containing) at least one of a cellulose ester resin, an acrylic resin, a cyclic olefin resin, and a polyethylene terephthalate resin. Can be preferably used. An optically isotropic film or an optically anisotropic retardation film may be used.
- any of the above optical films for example, Fujitac TD80UL (manufactured by FUJIFILM Corporation) or the like can be used as a film containing a cellulose ester resin.
- examples of the optical film containing an acrylic resin include an optical film containing a (meth) acrylic resin containing a styrene resin described in Japanese Patent No. 4570042, and a glutalimide ring described in Japanese Patent No. 5041532.
- An optical film containing a (meth) acrylic resin having a structure in the main chain an optical film containing a (meth) acrylic resin having a lactone ring structure described in JP-A-2009-1226664, JP-A-2009-139754
- An optical film containing a (meth) acrylic resin having the above-mentioned glutaric acid anhydride unit can be used.
- those containing a cyclic olefin resin include cyclic olefin resin films described in paragraphs [0029] and subsequent paragraphs of JP-A-2009-237376, Japanese Patent No. 4881827, JP-A-2008-.
- a cyclic olefin resin film containing an additive for reducing Rth described in Japanese Patent Application Laid-Open No. 063536 can be used. Further, any of the above optical films may contain an ultraviolet absorber. As the ultraviolet absorber, a commonly used compound can be used without particular limitation. The content of the ultraviolet absorber in the ultraviolet absorbing layer is appropriately adjusted according to the purpose.
- the wavelength selective absorption filter of the present invention has the above-mentioned gas barrier layer or any optical film in addition to the wavelength selective absorption filter of the present invention, from these wavelength selective absorption filters and the gas barrier layer and / or any optical film.
- the laminate can be produced by using the above-mentioned method for producing a wavelength selective absorption filter and the method for producing a gas barrier layer.
- a method of directly producing the above-mentioned gas barrier layer on the wavelength selective absorption filter produced by the above-mentioned production method can be mentioned.
- the above-mentioned arbitrary optical film it is also preferable to bond them via an adhesive layer.
- the display device of the present invention includes the wavelength selective absorption filter of the present invention.
- the display device of the present invention is configured to include the wavelength selective absorption filter of the present invention at a position that exhibits the external light reflection prevention function (when the gas barrier layer is included, the gas barrier layer is at least at least.
- the gas barrier layer is at least at least.
- other configurations can be used without particular limitation on the configuration of a commonly used display device.
- the display device is not particularly limited, but includes a light emitting diode such as an organic light emitting diode (OLED) display device, a micro light emitting diode (micro LED) display device, and a mini light emitting diode (mini LED) display device as a light emitting source.
- a light emitting diode such as an organic light emitting diode (OLED) display device, a micro light emitting diode (micro LED) display device, and a mini light emitting diode (mini LED) display device as a light emitting source.
- OLED organic light emitting diode
- micro LED micro light emitting diode
- mini LED mini LED
- the configuration example of the self-luminous display device is not particularly limited, but for example, glass, a layer including a TFT (thin film transistor), a light emitting element, a wavelength selective absorption filter of the present invention, and a surface thereof are ordered from the opposite side to external light.
- a display device including a film can be mentioned.
- the light source of the display light of the self-luminous display device may be a single blue color or may use the three primary colors of blue, green and red as long as it includes a light emitting diode as a light emitting source.
- the mini LED means an LED having a chip size of about 100 to 200 ⁇ m square
- the micro LED means an LED having a chip size of less than 100 ⁇ m square.
- the micro LED for example, the micro LED described in International Publication No. 2014/204694 and the like is preferably mentioned.
- the self-luminous display device is excellent in the absorbance of the dye contained in the wavelength selective absorption filter of the present invention even when the wavelength selective absorption filter of the present invention is provided as an antireflection means instead of the circular polarizing plate. Can be maintained at the same level. Further, when the dye contained in the wavelength selective absorption filter of the present invention is in the form of containing four kinds of dyes A to D in combination as described above, the light resistance is lowered due to the mixing of the dyes. It can show an excellent level of light resistance, which is higher than that of other products.
- the display device of the present invention including the self-luminous display device is circularly polarized.
- the above-mentioned excellent effect can be exhibited without using a plate. It should be noted that the display device (including the self-luminous display device) of the present invention does not prevent the use of the antireflection film in combination as long as the effect of the present invention is not impaired.
- the wavelength selective absorption filter of the present invention is preferably bonded to glass (base material) via an adhesive layer on a surface located on the side opposite to external light.
- the composition of the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer is not particularly limited, and for example, a pressure-sensitive adhesive composition containing a base resin having a mass average molecular weight (M w ) of 500,000 or more may be used. ..
- M w mass average molecular weight
- the upper limit of the mass average molecular weight of the base resin is not particularly limited, but if the mass average molecular weight is excessively increased, the coating property may be deteriorated due to the increase in viscosity, so 2,000,000 or less is preferable.
- the specific type of the base resin is not particularly limited, and examples thereof include acrylic resin, silicone resin, rubber resin, and EVA (ethylene-vinyl acetate) resin.
- acrylic resins are mainly used because of their excellent transparency, oxidation resistance, and resistance to yellowing, but they are not limited to this. do not have.
- acrylic resin examples include 80 parts by mass to 99.8 parts by mass of the (meth) acrylic acid ester monomer; and 0.02 parts by mass to 20 parts by mass of another crosslinkable monomer (preferably 0).
- a polymer of a monomer mixture containing (2 parts by mass to 20 parts by mass) can be mentioned.
- the type of the (meth) acrylic acid ester monomer is not particularly limited, and examples thereof include alkyl (meth) acrylates.
- alkyl (meth) acrylates In this case, if the alkyl group contained in the monomer becomes an excessively long chain, the cohesive force of the adhesive may decrease, and it may be difficult to control the glass transition temperature (T g ) or the adhesiveness. Therefore, carbon It is preferable to use a (meth) acrylic acid ester monomer having an alkyl group of several 1 to 14.
- Examples of such monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth).
- the (meth) acrylic acid ester monomer is preferably contained in an amount of 80 parts by mass to 99.8 parts by mass in 100 parts by mass of the monomer mixture.
- the content of the (meth) acrylic acid ester monomer is less than 80 parts by mass, the initial adhesive strength may decrease, and when it exceeds 99.8 parts by mass, the durability may decrease due to the decrease in cohesive force. be.
- crosslinkable monomers contained in the monomer mixture react with the polyfunctional crosslinking agent described later to impart a cohesive force to the adhesive, and have a role of adjusting the adhesive force and durability reliability.
- sexual functional groups can be imparted to the polymer.
- crosslinkable monomer include a hydroxy group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.
- Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl ( Examples thereof include meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate.
- Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyl acid, and acrylic acid dimer.
- Examples include itaconic acid, maleic acid and maleic acid anhydride.
- Examples of the nitrogen-containing monomer include (meth) acrylamide, N-vinylpyrrolidone or N-vinylcaprolactam. In the present invention, these crosslinkable monomers may be used alone or in combination of two or more.
- the other crosslinkable monomer may be contained in an amount of 0.02 part by mass to 20 parts by mass in 100 parts by mass of the monomer mixture.
- the content is less than 0.02 parts by mass, the durability reliability of the pressure-sensitive adhesive may decrease, and when it exceeds 20 parts by mass, at least one of the adhesiveness and the peelability may decrease.
- the method for producing a polymer using a monomer mixture is not particularly limited, and can be produced, for example, through a general polymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization. ..
- a solution polymerization method it is particularly preferable to use a solution polymerization method, and solution polymerization is preferably carried out at a polymerization temperature of 50 ° C. to 140 ° C. by mixing the initiator in a state where the respective monomers are uniformly mixed. ..
- Examples of the initiator used at this time include azo-based polymerization initiators such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile; and ordinary initiators such as peroxides such as benzoyl peroxide and acetyl peroxide. Be done.
- azo-based polymerization initiators such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile
- ordinary initiators such as peroxides such as benzoyl peroxide and acetyl peroxide. Be done.
- the pressure-sensitive adhesive composition may further contain 0.1 part by mass to 10 parts by mass of a cross-linking agent with respect to 100 parts by mass of the base resin.
- a cross-linking agent can impart cohesive force to the pressure-sensitive adhesive through a cross-linking reaction with the base resin.
- the content of the cross-linking agent is less than 0.1 parts by mass, the cohesive force of the pressure-sensitive adhesive may decrease. Further, if it exceeds 10 parts by mass, durability reliability may decrease due to delamination and floating phenomenon.
- the type of the cross-linking agent is not particularly limited, and any cross-linking agent such as an isocyanate-based compound, an epoxy-based compound, an aziridine-based compound, and a metal chelate-based compound can be used.
- Examples of the isocyanate-based compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate, and any compound and polyol (for example, trimethylolpropane).
- Examples of the epoxy compound include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N', N'-tetraglycidyl ethylenediamine and glycerin diglycidyl ether.
- examples thereof include melamine, bisprothaloyl-1- (2-methylaziridine) and tri-1-aziridinylphosphine oxide.
- the metal chelate compound include compounds in which at least one of polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and vanadium is coordinated with acetylacetone or ethyl acetoacetate. ..
- the pressure-sensitive adhesive composition may further contain 0.01 parts by mass to 10 parts by mass of a silane-based coupling agent with respect to 100 parts by mass of the base resin.
- the silane-based coupling agent can contribute to the improvement of adhesive reliability when the adhesive is left for a long time under high temperature or high humidity conditions, and particularly improves the adhesive stability when adhering to a glass substrate, and has heat resistance and heat resistance. Moisture resistance can be improved.
- silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and vinyltrimethoxy.
- These silane-based coupling agents may be used alone or in combination of two or more.
- the silane-based coupling agent is preferably contained in an amount of 0.01 parts by mass to 10 parts by mass, and further contained in an amount of 0.05 parts by mass to 1 part by mass with respect to 100 parts by mass of the base resin. preferable.
- the content is less than 0.01 parts by mass, the effect of increasing the adhesive strength may not be sufficient, and when it exceeds 10 parts by mass, durability reliability may be lowered such as bubbles or peeling phenomenon.
- the pressure-sensitive adhesive composition may further contain an antistatic agent, and as the antistatic agent, it has excellent compatibility with other components contained in the pressure-sensitive adhesive composition such as acrylic resin, and the transparency of the pressure-sensitive adhesive and work Any compound can be used as long as it does not adversely affect the properties and durability and can impart antistatic performance to the pressure-sensitive adhesive.
- the antistatic agent include inorganic salts and organic salts.
- the inorganic salt is a salt containing an alkali metal cation or an alkaline earth metal cation as a cation component.
- the cations include lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), cesium ion (Cs + ), beryllium ion (Be 2+ ), and magnesium ion (Be 2+).
- Li + lithium ion
- Na + sodium ion
- K + potassium ion
- Rb + rubidium ion
- Cs + cesium ion
- Be 2+ beryllium ion
- Be 2+ magnesium ion
- Mg 2+ calcium ion
- strontium ion (Sr 2+ ) and barium ion (Ba 2+ ) can be mentioned, preferably lithium ion (Li + ), sodium ion.
- Lithium ions are particularly preferred in terms of ion safety and mobility within the pressure-sensitive adhesive.
- the organic salt is a salt containing onium cation as a cation component.
- onium cation is a positive (+) charged ion in which at least a portion of the charge is ubiquitous in one or more atoms of nitrogen (N), phosphorus (P) and sulfur (S). Means.
- the onium cation is a cyclic or acyclic compound, and in the case of a cyclic compound, it can be a non-aromatic or aromatic compound. Further, in the case of a cyclic compound, one or more heteroatoms (for example, oxygen) other than nitrogen, phosphorus or sulfur atoms can be contained.
- the cyclic or non-cyclic compound is optionally substituted with a substituent such as a hydrogen atom, a halogen atom, an alkyl or an aryl.
- a substituent such as a hydrogen atom, a halogen atom, an alkyl or an aryl.
- the substituent may be a cyclic or acyclic substituent, aromatic or non-aromatic. It is a substitution product.
- the onium cation is preferably a cation containing a nitrogen atom, and more preferably an ammonium ion.
- Ammonium ions are quaternary ammonium ions or aromatic ammonium ions.
- the pressure-sensitive adhesive composition contains an antistatic agent in an amount of 0.01 parts by mass to 5 parts by mass, preferably 0.01 parts by mass to 2 parts by mass, and more preferably 0 parts by mass with respect to 100 parts by mass of the base resin. Includes 1 to 2 parts by mass. If the content is less than 0.01 parts by mass, the desired antistatic effect may not be obtained, and if it exceeds 5 parts by mass, the compatibility with other components is lowered and the durability and reliability of the adhesive are reduced. Or the transparency may deteriorate.
- the pressure-sensitive adhesive composition further comprises a compound capable of forming a coordinate bond with an antistatic agent, specifically, a cation contained in the antistatic agent (hereinafter, referred to as a "coordination bond compound").
- a coordination bond compound capable of forming a coordinate bond with an antistatic agent, specifically, a cation contained in the antistatic agent.
- the type of coordinate-binding compound that can be used is not particularly limited as long as it has a functional group capable of coordinating with an antistatic agent in the molecule, and examples thereof include alkylene oxide-based compounds.
- the alkylene oxide-based compound is not particularly limited, but an alkylene oxide-based compound containing an alkylene oxide unit having a basic unit having 2 or more carbon atoms, preferably 3 to 12, more preferably 3 to 8 carbon atoms is used. Is preferable.
- the alkylene oxide compound preferably has a molecular weight of 5,000 or less.
- the term "molecular weight” as used in the present invention means the molecular weight or mass average molecular weight of a compound. In the present invention, if the molecular weight of the alkylene oxide compound exceeds 5,000, the viscosity may be excessively increased and the coating property may be deteriorated, or the complex forming ability with the metal may be lowered.
- the lower limit of the molecular weight of the alkylene oxide compound is not particularly limited, but is preferably 500 or more, and more preferably 4,000 or more.
- an ester compound having one or more ether bonds disclosed in Korean Publication No. 2006-0018495 is disclosed in Korean Publication No. 2006-0128659.
- Various coordination-bonding compounds such as an oxalate group-containing compound, a diamine group-containing compound, a polyvalent carboxyl group-containing compound, and a ketone group-containing compound can be appropriately selected and used as necessary.
- the coordination-bonding compound is preferably contained in the pressure-sensitive adhesive composition in a proportion of 3 parts by mass or less with respect to 100 parts by mass of the base resin, more preferably 0.1 parts by mass to 3 parts by mass, and further preferably. , 0.5 parts by mass to 2 parts by mass. If the content exceeds 3 parts by mass, the physical properties of the pressure-sensitive adhesive such as peelability may deteriorate.
- the pressure-sensitive adhesive composition may further contain 1 part by mass to 100 parts by mass of the tackifying resin with respect to 100 parts by mass of the base resin. If the content of the tackifying resin is less than 1 part by mass, the addition effect may not be sufficient, and if it exceeds 100 parts by mass, at least one of the compatibility and the cohesive force improving effect may be lowered.
- the adhesive-imparting resin is not particularly limited, and is, for example, a (hydrogenated) hydrocarbon resin, a (hydrogenated) rosin resin, a (hydrogenated) rosin ester resin, and a (hydrogenated) terpene.
- Examples thereof include a resin, a (hydrogenated) terpene phenol resin, a polymerized rosin resin, and a polymerized rosin ester resin. These tackifying resins may be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition is a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator; an epoxy resin; a curing agent; an ultraviolet stabilizer; an antioxidant; a toning agent, as long as the effect of the invention is not affected. It may contain one or more additives such as a reinforcing agent; a filler; a defoaming agent; a surfactant; a photopolymerizable compound such as a polyfunctional acrylate; and a plasticizer.
- a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator
- an epoxy resin such as a curing agent; an ultraviolet stabilizer; an antioxidant; a toning agent, as long as the effect of the invention is not affected. It may contain one or more additives such as a reinforcing agent; a filler; a defoaming agent; a surfactant; a photopolymerizable compound such as
- the wavelength selective absorption filter of the present invention is preferably bonded to glass (base material) via an adhesive layer on a surface located on the side opposite to external light.
- the method for forming the pressure-sensitive adhesive layer is not particularly limited, and for example, a method of applying the pressure-sensitive adhesive composition to the wavelength selective absorption filter of the present invention by a usual means such as a bar coater, and drying and curing the pressure-sensitive adhesive composition; First, the adhesive layer is applied to the surface of the peelable base material and dried, and then the pressure-sensitive adhesive layer is transferred to the wavelength selective absorption filter of the present invention using the peelable base material, and aged and cured.
- the peelable base material is not particularly limited, and any peelable base material can be used, and examples thereof include the release film in the above-mentioned method for producing a wavelength selective absorption filter of the present invention.
- the conditions of application, drying, aging and curing can be appropriately adjusted based on a conventional method.
- ⁇ max means the maximum absorption wavelength showing the maximum absorbance in the measurement of the maximum absorbance value and the 20% value wavelength of the wavelength selective absorption filter described later.
- a wavelength selective absorption filter was produced according to the following procedure. The materials used to fabricate the wavelength selective absorption filter are shown below.
- ⁇ Matrix resin> (Resin 9) Apel APL6011T (trade name, manufactured by Mitsui Chemicals, a copolymer of ethylene and norbornene, Tg 105 ° C.), which is a cyclic polyolefin resin, was used as the resin 9.
- Arton RX4500 (trade name, manufactured by JSR Corporation, norbornene-based polymer, Tg 132 ° C.), which is a cyclic polyolefin resin, was used as the resin 10.
- association inhibitor The following compounds were used as association inhibitors.
- Base material 1 A cellulose acylate film (manufactured by Fuji Film Co., Ltd., trade name: ZRD40SL) was used as the base material 1.
- Base material 4 A polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, trade name: Diafoil T600E50, film thickness 50 ⁇ m) was used as the base material 4.
- the obtained wavelength selective absorption layer forming liquid A is filtered using a filter paper (# 63, manufactured by Toyo Filter Paper Co., Ltd.) having an absolute filtration accuracy of 10 ⁇ m, and further, a metal sintered filter (FH025,) having an absolute filtration accuracy of 2.5 ⁇ m. Filtered using Paul).
- Wavelength selective absorption filter with substrate No. 101 The wavelength selective absorption layer forming liquid A after the filtration treatment was applied onto the substrate 1 using a bar coater so that the film thickness after drying was 1.9 ⁇ m, and dried at 120 ° C. Wavelength selective absorption filter with substrate No. 101 was produced.
- Wavelength selective absorption filter with substrate No. Preparation of 102 to 109 and C201 to C204 Wavelength selective absorption filter with substrate except that at least one of the type and amount of dye and the type and amount of association inhibitor are changed to the contents shown in Table 1 below. No. Similar to the production of 101, the wavelength selective absorption filter No. 1 with a substrate was used. 102 to 109 and C201 to C204 were produced.
- the obtained wavelength selective absorption layer forming liquid B is filtered using a filter paper (# 63, manufactured by Toyo Filter Paper Co., Ltd.) having an absolute filtration accuracy of 10 ⁇ m, and further, a metal sintered filter (FH025,) having an absolute filtration accuracy of 2.5 ⁇ m. Filtered using Paul).
- Wavelength selective absorption filter with substrate No. 110 The wavelength selective absorption layer forming liquid B after the filtration treatment was applied onto the substrate 2 using a bar coater so that the film thickness after drying was 1.2 ⁇ m, and dried at 120 ° C. Wavelength selective absorption filter with substrate No. 110 was made.
- Wavelength selective absorption filter with substrate No. Preparation of 111-115, C205 and C206 Base materials except that at least one of the type of base material, the type and amount of dye added, and the type and amount of association inhibitor added are changed to the contents shown in Table 1 below. Wavelength selective absorption filter No. Similar to the production of 110, the wavelength selective absorption filter No. 1 with a substrate was used. 111-115, C205 and C206 were made.
- Wavelength selective absorption filter with substrate No. 101 to 115 are the wavelength selective absorption filters with a base material of the present invention
- the wavelength selective absorption filters with a base material No. C201 to C206 are wavelength selective absorption filters with a comparative substrate.
- the "-" notation in the dye column indicates that the corresponding dye is not contained.
- the content of the dye means the content ratio of the dye in the wavelength selective absorption filter on a mass basis, and the unit is mass%.
- the content of the association inhibitor means the content ratio of the association inhibitor in the wavelength selective absorption filter on a mass basis, and the unit is mass%.
- ⁇ max indicates the absorption maximum wavelength of the dye showing the maximum absorbance in the measurement of the maximum absorbance value and the 20% value wavelength of the wavelength selective absorption filter described later.
- Compound Example 5 Compound Example 5 used in Examples of International Publication No. 2014/208749.
- a laminated body of a gas barrier layer and a wavelength selective absorption filter (hereinafter, simply referred to as a laminated body) was produced according to the following procedure. The materials used for production are shown below.
- AQ-4104 manufactured by Kuraray Co., Ltd., Excelval AQ-4104 (trade name), modified polyvinyl alcohol (crystalline resin), saponification degree 98-99 mol%)
- Base material 3 Wavelength selective absorption filter with substrate No.
- the wavelength selective absorption filter side of 101 is subjected to corona treatment under the conditions of a discharge amount of 1000 W ⁇ min / m 2 and a treatment speed of 3.2 m / min using a corona treatment device (trade name: Corona-Plus, manufactured by VETAPHONE). It was applied and used as the base material 3.
- the obtained gas barrier layer forming liquid 1 was filtered using a filter with an absolute filtration accuracy of 5 ⁇ m (trade name: Hydrophobic Fluororemore Membrane, manufactured by Millex).
- the laminated body No. In the same manner as in the production of 101, the laminated body No. 102 to 115 and C202 to C204 were produced. Further, the type of the wavelength selective absorption filter with a substrate is referred to as the wavelength selective absorption filter with a substrate No. Except for changing to C201, the laminated body No. In the same manner as in the production of 101, the laminated body No. C201 is a type of wavelength selective absorption filter with a base material, and the wavelength selective absorption filter with a base material is No. Except for changing to C205, the laminated body No.
- the laminated body No. C205 is a type of wavelength selective absorption filter with a base material, and the wavelength selective absorption filter with a base material is No. Except for changing to C206, the laminated body No. In the same manner as in the production of 101, the laminated body No. C206 was prepared respectively.
- Laminated body No. 101 to 115 are laminated bodies containing the wavelength selective absorption filter of the present invention, and the laminated body No. C202 to C204 are comparative laminates, and the laminate No. C201, C205 and C206 are reference laminates.
- the gas barrier layer was peeled off by 2 to 3 mg from the laminate prepared above, and the temperature was raised at 10 ° C./min in the range of 20 ° C. to 260 ° C. using DSC7000X (trade name) manufactured by Hitachi High-Tech Science Co., Ltd. to melt it. Heat 1 was measured. J. Apple. Pol. Sci. , 81, 762 (2001), calculated the crystallinity of the gas barrier layer. Specifically, the above-mentioned heat of fusion 1 and J. Apple. Pol. Sci. , 81, 762 (2001), the heat of fusion 2 of the perfect crystal was used, and the crystallinity was calculated by the following formula.
- the laminated body No. In the production of 101 to 115 and C201 to C206, the laminated body was produced in the same manner except that the wavelength selective absorption filter was not subjected to the corona treatment. Next, a triacetyl cellulose film having a thickness of 80 ⁇ m (trade name: Fujitac TD80UL, manufactured by Soken Chemical Co., Ltd.) is interposed on the gas barrier layer side of the laminate via an adhesive 1 (trade name: SK2057, manufactured by Soken Chemical Co., Ltd.) having a thickness of about 20 ⁇ m. Made) were pasted together.
- a triacetyl cellulose film having a thickness of 80 ⁇ m (trade name: Fujitac TD80UL, manufactured by Soken Chemical Co., Ltd.) is interposed on the gas barrier layer side of the laminate via an adhesive 1 (trade name: SK2057, manufactured by Soken Chemical Co., Ltd.) having a thickness of about 20 ⁇ m. Made) were pasted together.
- Oxygen permeability evaluation film No. L101 to L115 and LC201 to LC206 were prepared. Using OX-TRAN 2/21 (trade name) manufactured by MOCON as an oxygen permeability measuring device, 25 ° C., relative humidity 50%, oxygen partial pressure 1 atm, measurement area 50 cm by the isobaric method (JIS K 7126-2). The oxygen permeability of the oxygen permeability evaluation film was measured under the condition of 2 . The laminated body No. measured in this way. The oxygen permeability of L101 to L115 and LC201 to LC206 was 0.6 cc / m 2 ⁇ day ⁇ atm.
- the wavelength selective absorption filter No. 1 with a base material In 101 to 109 and C202 to C204, No. 1 as a wavelength selective absorption filter with a substrate containing no dye.
- the wavelength selective absorption filter with a substrate of C201 the wavelength selective absorption filter with a substrate No. In 110 to 112, No. 1 as a wavelength selective absorption filter with a substrate containing no dye.
- the wavelength selective absorption filter with a substrate of C205 the wavelength selective absorption filter with a substrate No. In 113 to 115, No. 1 was used as a wavelength selective absorption filter with a substrate containing no dye.
- a wavelength selective absorption filter with a substrate of C206 was used.
- the maximum absorption wavelength ⁇ max was determined based on the above Ab x ( ⁇ ) ⁇ Ab 0 ( ⁇ ). (Determination of 20% value wavelength) Subsequently, in the above-mentioned Ab x ( ⁇ ) -Ab 0 ( ⁇ ), when a dye having a main absorption wavelength band at a wavelength of 390 to 440 nm is contained, the absorbance is 20% of the maximum absorbance at a wavelength of 390 to 440 nm. Of the two wavelengths that give absorbance, the wavelength on the long wavelength side (20% value wavelength A) was determined.
- Light resistance evaluation film A 60 ⁇ m-thick triacetyl cellulose film (trade name: Fujitac TG60UL, manufactured by Fujifilm Co., Ltd.) is placed on the gas barrier layer side of the laminate via an adhesive 1 (trade name: SK2057, manufactured by Soken Chemical Co., Ltd.) having a thickness of about 20 ⁇ m. I pasted them together. Subsequently, the base material 1, the base material 2 or the base material 4 is peeled off, and the glass is attached to the wavelength selective absorption filter side to which the base material 1, the base material 2 or the base material 4 is attached via the above-mentioned adhesive 1. Then, a light resistance evaluation film was prepared. The obtained light resistance evaluation film has a structure in which glass / adhesive 1 layer / wavelength selective absorption filter / gas barrier layer / adhesive 1 layer / triacetyl cellulose film are laminated in this order.
- the absorbance of the light resistance evaluation film in the wavelength range of 200 to 1000 nm was measured for each 1 nm using a UV3600 spectrophotometer (trade name) manufactured by Shimadzu Corporation.
- the absorbance difference between the absorbance at each wavelength of the light resistance evaluation film and the absorbance of the light resistance evaluation film having the same configuration except that it does not contain a dye and an association inhibitor is calculated, and the maximum value of this absorbance difference is the maximum absorption value.
- the laminated body No. In the light resistance evaluation films of 101 to 109 and C202 to C204, the laminated body No. 1 containing no dye and association inhibitor.
- the absorbance difference was calculated using the light resistance evaluation film of C201, and the laminate No. In the light resistance evaluation films of 110 to 112, the laminated body No. 1 containing no dye and association inhibitor.
- the absorbance difference was calculated using the light resistance evaluation film of C205, and the laminate No. In the light resistance evaluation films of 113 to 115, the laminate No. 1 containing no dye and association inhibitor.
- the absorbance difference was calculated using the light resistance evaluation film of C206.
- the comparative laminate No. 1 containing no association inhibitor is contained.
- the 20% value wavelength A was 456 nm, which was outside the range specified in the present invention, and the residual rate after irradiation with xenon for 200 hours was as low as 73%.
- the 20% value wavelength A is 465 nm, which is outside the range specified in the present invention.
- C204 had a low residual rate of 73% after irradiation with xenon for 200 hours.
- the laminate No. 1 which contains the dye A and the association inhibitor specified in the present invention and has a 20% value wavelength A of 455 nm or less.
- the residual rate of dye A after irradiation with xenon for 200 hours was 79% or more, showing excellent light resistance.
- the comparative laminate No. 1 containing no association inhibitor is contained.
- the 20% value wavelength D was 639 nm, which was outside the range specified in the present invention, and the residual rate after 200 hours of xenon irradiation was 91%.
- No. 1 using a carboxylic acid amide compound as an association inhibitor Among 105 to 107, No. 1 using an association inhibitor having a cyclohexane ring. No. 107 has a light resistance of 87% and uses an association inhibitor having a benzene ring. The light resistance of 106 is 92%, and No. 1 using an association inhibitor having no ring structure. It can be seen that better light resistance is obtained as compared with 105.
- Wavelength selective absorption filter Wavelength selective absorption layer
- Gas barrier layer 93
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Abstract
Description
しかし、ディスプレイに入射した光のうち、一部は表面の反射防止フィルム又は防眩フィルムを透過し、電極もしくは配線等の表面又はセルのガラス表面で反射する。これは内部反射と呼ばれる。ディスプレイの高精細化に伴い、電極又は配線等の金属部分の面積のパネル全体の面積に占める割合(電極又は配線等の金属部分の面積/パネル全体の面積)が高まるため、上記内部反射の防止は高品位の表示性能を確保する上で特に重要な因子となる。
例えば、特許文献2では、視認者側偏光板中に、半値幅が50nm以下である吸光度のピークを持つ吸収材料であって、470~510nmの波長帯域に吸光度の最大値を有する第1の吸収材料および560~610nmの波長帯域に吸光度の最大値を有する第2の吸収材料の少なくとも一方の吸収材料を添加することにより、外光の反射を防止する方法を用いた液晶表示装置が開示されている。
また、特許文献3では、画像表示装置、特にプラズマディスプレイのような自発光型の画像表示装置に対して、明所でのコントラスト低下の抑制と色再現改良を目的として、380nm乃至420nmの波長領域、480nm乃至520nmの波長領域、および585nm乃至620nmの波長領域に、それぞれ吸収極大を有する光学フィルタを用いることが提案されている。
本発明者らが検討を重ねたところ、上記特許文献2に記載の技術では、液晶表示装置等の偏光板が必須であるディスプレイにおいては有望な方法であるものの、上記自発光表示装置に適用した場合には、偏光板を有しないために吸収材が偏光子で覆われず、吸収材が光によって劣化しやすくなる問題があること、すなわち、耐光性の観点から改良が必要であることがわかってきた。また、上記特許文献3に記載の方法も吸収材が光によって劣化しやすい問題があり、耐光性の観点から改良が必要であることがわかってきた。
また上記特許文献4又は5記載の光学フィルム又は硬化膜においても耐光性が不十分であり、改良が求められていた。
<1>
樹脂と、色素と、カルボン酸エステル結合、カルボン酸アミド結合、スルホン酸アミド結合、ウレタン結合及びスルホニル結合の少なくともいずれか1つの極性基を有し、分子量が1000以下である化合物とを含み、
上記色素が、下記に示す染料A及び染料Dの少なくとも一方を含み、
上記染料Aを含む場合は、波長390~440nmにおける吸光度極大値に対して、20%の吸光度を与える二つの波長のうち長波長側の波長が455nm以下であり、
上記染料Dを含む場合は、波長680~780nmにおける吸光度極大値に対して、20%の吸光度を与える二つの波長のうち短波長側の波長が640nm以上である、
波長選択吸収フィルタ。
染料A:波長390~440nmに主吸収波長帯域を有する色素
染料D:波長680~780nmに主吸収波長帯域を有する色素
<2>
上記色素が、上記染料Aおよび上記染料Dの両方を含む、<1>に記載の波長選択吸収フィルタ。
<3>
上記染料Aが下記一般式(A1)で表される色素である、<1>又は<2>に記載の波長選択吸収フィルタ。
<4>
上記染料Dが下記一般式(1)で表されるスクアリン系色素である、<1>~<3>のいずれか1つに記載の波長選択吸収フィルタ。
<5>
上記の極性基を有する化合物が、カルボン酸エステル結合を有する化合物である、<1>~<4>のいずれか1つに記載の波長選択吸収フィルタ。
<6>
上記の極性基を有する化合物が、カルボン酸アミド結合を有する化合物である、<1>~<4>のいずれか1つに記載の波長選択フィルタ
<7>
上記樹脂がポリスチレン樹脂を含む、<1>~<6>のいずれか1つに記載の波長選択吸収フィルタ。
<8>
上記樹脂が環状ポリオレフィン樹脂を含む、<1>~<6>のいずれか1つに記載の波長選択吸収フィルタ。
<9>
<1>~<8>のいずれか1つに記載の波長選択吸収フィルタを含む表示装置。
<10>
上記表示装置が自発光表示装置である、<9>に記載の表示装置。
本発明において、ある基の炭素数を規定する場合、この炭素数は、本発明ないし本明細書において特段の断りのない限りは、基全体の炭素数を意味する。つまり、この基がさらに置換基を有する形態である場合、この置換基を含めた全体の炭素数を意味する。
本発明において、特段の断りがない限り、波長選択吸収フィルタを構成する成分(染料、樹脂、会合抑制剤及びその他の成分等)は、それぞれ、波長選択吸収フィルタ中に1種含有されていてもよく、2種以上含有されていてもよい。同様に、特段の断りがない限り、ガスバリア層を構成する成分(結晶性樹脂等)は、それぞれ、ガスバリア層中に1種含有されていてもよく、2種以上含有されていてもよい。
本発明において、特段の断りがない限り、二重結合については、分子内にE型及びZ型が存在する場合、そのいずれであっても、またこれらの混合物であってもよい。
本発明において、化合物(錯体を含む。)の表示については、化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、本発明の効果を損なわない範囲で、構造の一部を変化させたものを含む意味である。更に、置換又は無置換を明記していない化合物については、本発明の効果を損なわない範囲で、任意の置換基を有していてもよい意味である。このことは、置換基及び連結基についても同様である。
また、本発明において「~」を用いて表される数値範囲は、「~」前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本発明において、組成物とは、成分濃度が一定である(各成分が均一に分散している)混合物に加えて、目的とする機能を損なわない範囲で成分濃度が変動している混合物を包含する。
本発明において、波長XX~YYnmに主吸収波長帯域を有するとは、極大吸収を示す波長(すなわち、極大吸収波長)が波長領域XX~YYnmに存在することを意味する。
したがって、この極大吸収波長が上記波長領域内にあれば、この波長を含む吸収帯域全体が上記波長領域内にあってもよく、上記波長領域外まで広がっていてもよい。また、極大吸収波長が複数存在する場合、最も大きい吸光度を示す極大吸収波長が上記波長領域に存在していればよい。すなわち、最も大きい吸光度を示す極大吸収波長以外の極大吸収波長は、上記波長領域XX~YYnmの内外のいずれに存在していてもよい。
本発明において、染料が有する主吸収波長帯域とは、波長選択吸収フィルタの状態で測定される染料の主吸収波長帯域である。具体的には、後述する実施例において、波長選択吸収フィルタの吸光度極大値および20%値波長の項に記載の条件により、波長選択吸収フィルタの状態で測定される。
また、本発明において、波長XX~YYnmにおける吸光度極大値とは、上記の波長XX~YYnmに存在する極大吸収波長における吸光度を意味し、吸収極大値とも称す。
また、波長XX~YYnmにおける吸光度極大値に対して20%の吸光度を与える二つの波長とは、波長XX~YYnmにおける吸光度極大値を最大吸光度とする吸収ピークにおいて、吸光度極大値を示す極大吸収波長の両側(短波長側及び長波長側)に位置する、この吸光度極大値の20%強度の吸光度を示す波長を意味する。なお、上記吸光度極大値を示す極大吸収波長の長波長側に位置する波長とは、上記極大吸収波長よりも長波長側に位置し、かつ、上記吸光度極大値の20%強度の吸光度を示す最も短波の波長を意味する。同様に、上記吸光度極大値を示す極大吸収波長の短波長側に位置する波長とは、上記極大吸収波長よりも短波長側に位置し、かつ、上記吸光度極大値の20%強度の吸光度を示す最も長波の波長を意味する。
本発明において、染料が有する吸光度極大値及びこの吸光度極大値に対して20%の吸光度を与える二つの波長とは、波長選択吸収フィルタの状態で測定される値である。具体的には、後述する実施例において、波長選択吸収フィルタの吸光度極大値および20%値波長の項に記載の条件により、波長選択吸収フィルタの状態で測定される。
また、本発明の表示装置は、上記耐光性に優れた波長選択吸収フィルタを含む。
本発明の波長選択吸収フィルタ(以下、波長選択吸収層とも称す。)は、樹脂と、色素と、カルボン酸エステル結合、カルボン酸アミド結合、スルホン酸アミド結合、ウレタン結合及びスルホニル結合の少なくともいずれか1つの極性基(本発明において「基」は「結合」を含む意味である)を有し、分子量が1000以下である化合物(会合抑制剤)とを含有し、上記色素は、異なる波長域に主吸収波長帯域を有する下記染料Aおよび染料Dの少なくとも一方を含有する。
染料A:波長390~440nmに主吸収波長帯域を有する染料
染料D:波長680~780nmに主吸収波長帯域を有する染料
本発明の波長選択吸収フィルタは、さらに、下記染料B及びCの少なくとも一方を含有してもよい。
染料B:波長480~520nmに主吸収波長帯域を有する染料
染料C:波長580~620nmに主吸収波長帯域を有する染料
上記波長選択吸収フィルタ中において、上記「染料」は、上記樹脂中に分散(好ましくは溶解)することにより、波長選択吸収フィルタを染料に由来する特定の吸収スペクトルを示すフィルタとするものである。
このように本発明の波長選択吸収フィルタは、耐光性に優れるため、表示装置に適用した場合にも優れた耐光性を示すことができる。また、特許文献2又は3に記載のように、含有させる染料を調整した波長選択吸収フィルタを表示装置に適用することにより、優れた耐光性を示しつつ、外光反射の抑制と輝度低下の抑制の両立でき、また、表示画像の色味への影響も十分に抑えることができる。
本発明の波長選択吸収フィルタは、上記の染料Aおよび染料Dの少なくとも一方を含有するフィルタ(層)である。
なお、本発明の波長選択吸収フィルタが上記染料Aを含有する場合、本発明の波長選択吸収フィルタ中に含有される上記染料Aは、1種でもよく、2種以上であってもよい。また、本発明の波長選択吸収フィルタが上記染料Dを含有する場合、本発明の波長選択吸収フィルタ中に含有される上記染料Dは、1種でもよく、2種以上であってもよい。本発明の波長選択吸収フィルタ中に含有され得る上記の染料B又は染料Cについても、染料A及び染料Dと同様に、各々独立に、1種でもよく、2種以上であってもよい。
本発明の波長選択吸収フィルタは上記染料A~D以外の染料を含有することもできる。
本発明の波長選択吸収フィルタが染料Aを含む場合、上記20%値波長Aは455nm以下であり、本発明の波長選択吸収フィルタが染料Dを含む場合、上記20%値波長Dは640nm以上である。
本発明の波長選択吸収フィルタは、反射防止と輝度低下の抑制の両立の観点からは、20%値波長Aは下記関係式(I)を満たすことが好ましく、20%値波長Dは下記関係式(II)を満たすことが好ましい。
関係式(I) 410nm≦20%値波長A≦455nm
上記関係式(I)において、20%値波長Aの上限値は、453nm以下が好ましく、450nm以下がより好ましい。下限値は、415nm以上が好ましく、420nm以上がより好ましい。
関係式(II) 640nm≦20%値波長D≦700nm
関係式(II)において、20%値波長Dの上限値は、690nm以下が好ましく、680nm以下がより好ましい。下限値は、645nm以上が好ましく、650nm以上がより好ましい。
染料Aは、波長選択吸収フィルタ中で波長390~440nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができ、波長選択吸収フィルタ中において、波長395~430nmに主吸収波長帯域を有するものが好ましく、波長400~430nmに主吸収波長帯域を有するものがより好ましい。
(置換基群A)
ハロゲン原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシ基、ニトロ基、カルボキシル基(塩の形でもよい)、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、スルホニルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基(-NH2の他、-NRa 2で表される置換アミノ基を含む。Raは、各々独立に、水素原子、アルキル基、アリール基又はヘテロアリール基を示す。ただし、少なくとも1つのRaは、アルキル基、アリール基又はヘテロアリール基である。)、アシルアミノ基、アミノカルボニルアミノ基、アルキルカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、スルホンアミド基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基(塩の形でもよい)、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基及びシリル基、並びに、これらの少なくとも2つが連結した一価の基。
置換アルキル基の総炭素数とは、置換アルキル基が有し得る置換基を含めた、置換アルキル基全体の炭素数を意味する。以下、その他の基においても同様の意味で使用する。
上記置換基群Aの中でも、置換アリール基が有し得る置換基の好ましい例としては、ハロゲン原子(例えば、塩素原子、臭素原子及びヨウ素原子)、ヒドロキシ基、カルボキシ基、スルホンアミド基、アミノ基(好ましくは、-NRa 2で表される置換アミノ基。Raは、各々独立に、水素原子又はアルキル基を示す。ただし、少なくとも1つのRaは、アルキル基である。炭素数は1~4が好ましい。)、アルキル基(好ましくは、炭素数1~4のアルキル基;例えば、メチル、エチル、ノルマルプロピル及びイソプロピル)、アルコキシ基(好ましくは、炭素数1~4のアルコキシ基;例えば、メトキシ、エトキシ、ノルマルプロポキシ及びイソプロポキシ)、アルコキシカルボニル基(好ましくは、炭素数2~5のアルコキシカルボニル基;例えば、メトキシカルボニル、エトキシカルボニル、ノルマルプロポキシカルボニル及びイソプロポキシカルボニル)及びスルホニルオキシ基、並びに、これらの少なくとも2つが連結した一価の基が挙げられる。
例えば、4-クロロフェニル基、2,5-ジクロロフェニル基、ヒドロキシフェニル基、4-カルボキシフェニル基、3,5-ジカルボキシフェニル基、4-メタンスルホンアミドフェニル基、4-メチルフェニル基、4-メトキシフェニル基、4-(2-ヒドロキシエトキシ)フェニル基、N,N-ジメチルアミノフェニル基、4-(N-カルボキシメチル-N-エチルアミノ)フェニル基、4-エトキシカルボニルフェニル基及び4-メタンスルホニルオキシフェニル基が挙げられる。
上記置換基群Aの中でも、R3、R5及びR6は、アルキル基又はアリール基が好ましい。すなわち、R3、R5及びR6としては、各々独立に、水素原子、アルキル基又はアリール基であることが好ましい。
また、上記置換基群Aの中では、R4は、アルキル基又はアリール基が好ましい。すなわち、R4としては、水素原子、アルキル基又はアリール基であることが好ましい。
上記R3、R5及びR6における置換アルキル基が有し得る置換基の好ましい例としては、アリール基(好ましくはフェニル基)、ハロゲン原子、アシル基、アミノ基、アルコキシカルボニル基、カルボキシ基及びヒドロキシ基が挙げられる。
上記R3、R5及びR6として採りうる置換アルキル基の総炭素数は1~8が好ましい。例えば、ベンジル基、カルボキシメチル基及びヒドロキシメチル基が挙げられる。
上記R3、R5及びR6における置換アリール基が有し得る置換基の好ましい例としては、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子)、ヒドロキシ基、カルボキシ基、並びに、アルキル基(好ましくは、炭素数1~4のアルキル基;例えば、メチル、エチル、ノルマルプロピル及びイソプロピル)が挙げられる。
なお、R3、R5及びR6がいずれもアリール基である場合、アリール基は同一でも異なっていてもよい。
上記R4における置換アルキル基が有し得る置換基の好ましい例としては、アリール基(好ましくはフェニル基)、ヘテロ環基、カルボキシ基、ヒドロキシ基、アルキル基(好ましくは、炭素数1~4のアルキル基;例えば、メチル、エチル、ノルマルプロピル及びイソプロピル)、アルコキシ基(好ましくは、炭素数1~4のアルコキシ基;例えば、メトキシ、エトキシ、ノルマルプロポキシ及びイソプロポキシ)、アリールオキシ基、アルコキシカルボニル基(好ましくは、炭素数2~5のアルコキシカルボニル基;例えば、メトキシカルボニル、エトキシカルボニル、ノルマルプロポキシカルボニル及びイソプロポキシカルボニル)、アルキルアミノ基(好ましくは炭素数1~4のアルキルアミノ基;例えば、ジメチルアミノ基)、アルキルカルボニルアミノ基(好ましくは炭素数1~4のアルキルカルボニルアミノ基;例えば、メチルカルボニルアミノ基)、シアノ基及びアシル基(例えばアセチル基、プロピオニル基、ベンゾイル基、メシル基)、並びに、これらの少なくとも2つが連結した一価の基が挙げられる。
例えば、ベンジル基、カルボキシベンジル基、ヒドロキシベンジル基、メトキシカルボニルエチル基、エトキシカルボニルメチル基、2-シアノエチル基、2-プロピオニルアミノエチル基、ジメチルアミノメチル基、メチルカルボニルアミノプロピル基、ジ(メトキシカルボニルメチル)アミノプロピル基及びフェナシル基が挙げられる。
上記R4における置換アリール基が有し得る置換基の好ましい例としては、ハロゲン原子(例えば、塩素原子、臭素原子、ヨウ素原子)、ヒドロキシ基、カルボキシ基、スルホンアミド基、アミノ基、アルキル基(好ましくは、炭素数1~4のアルキル基;例えば、メチル、エチル、ノルマルプロピル、イソプロピル)、アルコキシ基(好ましくは、炭素数1~4のアルコキシ基;例えば、メトキシ、エトキシ、ノルマルプロポキシ、イソプロポキシ)、アルコキシカルボニル基(好ましくは、炭素数2~5のアルコキシカルボニル基;例えば、メトキシカルボニル、エトキシカルボニル、ノルマルプロポキシカルボニル、イソプロポキシカルボニル)及びスルホニルオキシ基、並びに、これらの少なくとも2つが連結した一価の基等が挙げられる。
上記R4における置換アリール基が有し得るアミノ基(-NRa 2)は、Raとして、上記R4における置換アルキル基と同様の基を挙げることができる。
上記置換アミノ基としては、アミノ基の水素原子の1つ又は2つがアルキル基で置換されたアルキルアミノ基が好ましい。
アルキルアミノ基としては、例えば、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基及びピロリジノ基が挙げられる。アルキルアミノ基の炭素数は1~8が好ましく、1~4がより好ましい。
また、アルキルアミノ基におけるアルキル基が更に置換されていてもよく、例えば、ジ(アルコキシカルボニルアルキル)アミノ基が好ましく挙げられる。ジ(アルコキシカルボニルアルキル)アミノ基の炭素数は6~10が好ましく、6~8がより好ましい。
R5とR6が互いに結合して形成される6員環は、ベンゼン環が好ましい。
R1及びR2が各々独立にアリール基を表す場合、R3、R5及びR6は、各々独立に、水素原子、アルキル基又はアリール基であって、かつ、R3及びR6の少なくとも一方は水素原子であることが好ましい。中でも、耐熱性及び耐光性の観点から、R3が水素原子を表し、R5及びR6が各々独立にアルキル基又はアリール基を表す場合がより好ましく、R3が水素原子を表し、R5及びR6が各々独立にアルキル基を表す場合が更に好ましく、R3が水素原子を表し、R5及びR6が各々独立にアルキル基を表し、かつ、R5及びR6が互いに結合して環を形成してピロール環に縮合し、ピロール環と共にインドール環を形成している場合が特に好ましい。即ち、上記一般式(A1)で表される色素は、下記一般式(A2)で表される色素であることが特に好ましい。
R15として採り得るアルキル基及びアリール基は、R3、R5及びR6として採り得るアルキル基及びアリール基の記載をそれぞれ適用することができる。
R15として採り得るハロゲン原子としては、例えば、塩素原子、臭素原子及びヨウ素原子が挙げられる。
R15として採り得るアシル基としては、例えば、アセチル基、プロピオニル基及びブチロイル基が挙げられる。
R15として採り得るアミノ基としては、R4における置換アリール基が有し得るアミノ基の記載を適用することができる。また、アミノ基の窒素原子上のアルキル基が結合して環を形成した、5~7員環の含窒素複素環基も好ましい。
R15として採り得るアルコキシカルボニル基としては、炭素数2~5のアルコキシカルボニル基が好ましく、例えば、メトキシカルボニル、エトキシカルボニル、ノルマルプロポキシカルボニル及びイソプロポキシカルボニルが挙げられる。
下記具体例において、Meはメチル基を示す。
染料Bは、波長選択吸収フィルタ中で波長480~520nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
また、染料Cは、波長選択吸収フィルタ中で波長580~620nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
染料Cの具体例としては、例えば、テトラアザポルフィリン(tetraaza porphyrin、TAP)系、スクアリン系及びシアニン(cyanine、CY)系の各色素(染料)が挙げられる。
すなわち、本発明の波長選択吸収フィルタは、上記色味変化の抑制の観点から、染料B及び染料Cの少なくとも一方がスクアリン系色素(好ましくは、国際公開第2019/189463号の[0016]~[0070]に記載の一般式(1)で表されるスクアリン系色素)であることが好ましく、染料B及び染料Cの両方がスクアリン系色素(好ましくは、国際公開第2019/189463号の[0016]~[0070]に記載の一般式(1)で表されるスクアリン系色素)であることがより好ましい。
なお、国際公開第2019/189463号における染料Aの記載は本発明における染料Bとして読み替え、国際公開第2019/189463号における染料Bの記載は本発明における染料Cとして読み替えるものとする。
下記具体例において、Meはメチル、Etはエチル、Buはブチル、Phはフェニルをそれぞれ示す。
下記具体例において、Meはメチル、Etはエチル、i-Prはiso-プロピル、t-Buはt-ブチル、Phはフェニルをそれぞれ示す。下記構造において*は各一般式中の炭素四員環との結合部を示す。
国際公開第2019/189463号記載の一般式(1)で表されるスクアリン系色素は、連結基を介して、共有結合により消光剤部が色素に連結されてなる、消光剤内蔵型色素であってもよい。上記消光剤内蔵型色素も、染料B及びCの少なくとも一方の色素として好ましく用いることができる。すなわち、上記消光剤内蔵型色素は、主吸収波長帯域を有する波長に応じて、染料B又は染料Cとして計上する。
上記消光剤部としては、例えば、後述の置換基Xにおけるメタロセニル基が挙げられる。なお、後述の置換基Xにおけるメタロセニル基の記載において、「一般式(1)」は「国際公開第2019/189463号記載の一般式(1)」に読み替えるものとする。
また、国際公開第2019/066043号の段落[0199]~[0212]および段落[0234]~[0310]に記載の消光剤化合物における消光剤部を挙げることができる。
すなわち、国際公開第2019/189463号記載の一般式(1)で表されるスクアリン系色素において、置換基Xとして上記消光剤部を有する色素も好ましい形態の1つである。
下記具体例において、Meはメチル、Etはエチル、Buはブチルをそれぞれ示す。
染料Dは、波長選択吸収フィルタ中で波長680~780nmに主吸収波長帯域を有するものであれば特に制限されず、各種染料を用いることができる。
本発明において、下記の各一般式で表される色素において、カチオンは非局在化して存在しており、複数の互変異性体構造が存在する。そのため、本発明において、ある色素の少なくとも1つの互変異性体構造が各一般式に当てはまる場合、ある色素は各一般式で表される色素とする。したがって、特定の一般式で表される色素とは、その少なくとも1つの互変異性体構造を特定の一般式で表すことができる色素ということもできる。本発明において、一般式で表される色素は、その互変異性体構造の少なくとも1つがこの一般式に当てはまる限り、どのような互変異性体構造をとるものでもよい。
A、B及びGは、それぞれ、置換基Xを有していてもよく、置換基Xを有する場合には、隣接する置換基が互いに結合してさらに環構造を形成してもよい。また、置換基Xは複数個存在してもよい。隣接する置換基Xが互いに結合してさらに環構造を形成する場合、2つの置換基Xがホウ素原子等のヘテロ原子を間に介して環を形成してもよい。このホウ素原子は、さらに置換基で置換されていてもよく、アルキル基及びアリール基等の置換基が挙げられる。2つの置換基Xが結合して形成される環の例としては、例えば、2つの下記-NR14R15が結合して形成される環、2つの下記-NR14R15がホウ素原子を間に介して結合して形成される環が挙げられる。
置換基Xとしては、例えば、以下の基が挙げられる。
アルキル基(炭素数は、1~20が好ましく、1~15がより好ましく、1~8がさらに好ましい。例えば、メチル、エチル、プロピル、イソプロピル、ブチル、t-ブチル、イソブチル、ペンチル、ヘキシル、オクチル、ドデシル、トリフルオロメチル、シクロペンチル、シクロヘキシル。)、
アルケニル基(炭素数は、2~20が好ましく、2~12がより好ましく、2~8がさらに好ましい。例えば、ビニル、アリル。)、
アルキニル基(炭素数は、2~40が好ましく、2~30がより好ましく、2~25が特に好ましい。例えば、エチニル、プロパルギル。)、
アリール基(炭素数は、6~30が好ましく、6~20がより好ましく、6~12がさらに好ましい。例えば、フェニル、ナフチル。)、
ヘテロ環基(芳香族ヘテロ環基及び脂肪族ヘテロ環基を含む。単環又は縮合環からなる基を含み、単環、又は環数が2~8個の縮合環からなる基が好ましく、単環又は環数が2~4個の縮合環からなる基がより好ましい。環を構成するヘテロ原子の数は1~3が好ましく、環を構成するヘテロ原子は、窒素原子、酸素原子又は硫黄原子等が挙げられ、5員環又は6員環からなる基が好ましい。ヘテロアリール基の環を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12がさらに好ましい。例えば、フリル、チエニル、ピリジル、ピリダジル、ピリミジル、ピラジル、トリアジル、イミダゾリル、ピラゾリル、チアゾリル、ベンゾイミダゾリル、ベンゾオキサゾリル、キナゾリル、フタラジル、ピロリジル、イミダゾリジル、モルホリル、オキサゾリジル。)、
アラルキル基(アラルキル基のアルキル部分は、上記アルキル基と同様である。アラルキル基のアリール部分は、上記アリール基と同様である。アラルキル基の炭素数は、7~40が好ましく、7~30がより好ましく、7~25がさらに好ましい。)、
メタロセニル基、
-OR10(例えば、ヒドロキシ基、アルコキシ基(メトキシ、エトキシ、プロピルオキシ等)、シクロアルコキシ基(シクロペンチルオキシ、シクロヘキシルオキシ等)、アリールオキシ基(フェノキシ、ナフチルオキシ等)、ヘテロアリールオキシ基(芳香族ヘテロ環オキシ基)が挙げられる。)、
-C(=O)R11(アセチル、エチルカルボニル、プロピルカルボニル、シクロヘキシルカルボニル、オクチルカルボニル、2-エチルヘキシルカルボニル、フェニルカルボニル、ナフチルカルボニル、ピリジルカルボニル等のアシル基が挙げられる。)、
-C(=O)OR12(例えば、カルボキシ基、アルコキシカルボニル基(メチルオキシカルボニル、エチルオキシカルボニル、ブチルオキシカルボニル、オクチルオキシカルボニル等)、アリールオキシカルボニル基(フェニルオキシカルボニル、ナフチルオキシカルボニル等)が挙げられる。)、
-OC(=O)R13(アセチルオキシ、エチルカルボニルオキシ、ブチルカルボニルオキシ、オクチルカルボニルオキシ、フェニルカルボニルオキシ等のアシルオキシ基が挙げられる。)、
-NR14R15(アミノ(-NH2)、エチルアミノ、ジメチルアミノ、ブチルアミノ、ジブチルアミノ、シクロペンチルアミノ、2-エチルヘキシルアミノ、ドデシルアミノ、アニリノ、ナフチルアミノ、2-ピリジルアミノ等のアミノ基が挙げられる。)、
-NHCOR16(メチルカルボニルアミノ、エチルカルボニルアミノ、ジメチルカルボニルアミノ、プロピルカルボニルアミノ、ペンチルカルボニルアミノ、シクロヘキシルカルボニルアミノ、2-エチルヘキシルカルボニルアミノ、オクチルカルボニルアミノ、ドデシルカルボニルアミノ、フェニルカルボニルアミノ、ナフチルカルボニルアミノ等のアミド基が挙げられる。)、
-CONR17R18(アミノカルボニル、メチルアミノカルボニル、ジメチルアミノカルボニル、プロピルアミノカルボニル、ペンチルアミノカルボニル、シクロヘキシルアミノカルボニル、オクチルアミノカルボニル、2-エチルヘキシルアミノカルボニル、ドデシルアミノカルボニル、フェニルアミノカルボニル、ナフチルアミノカルボニル、2-ピリジルアミノカルボニル等のカルバモイル基が挙げられる。)、
-NHCONR19R20(メチルウレイド、エチルウレイド、ペンチルウレイド、シクロヘキシルウレイド、オクチルウレイド、ドデシルウレイド、フェニルウレイド、ナフチルウレイド、2-ピリジルアミノウレイド等のウレイド基が挙げられる。)、
-NHCOOR21、
-SR22(例えば、アルキルチオ基(メチルチオ、エチルチオ、プロピルチオ等)、シクロアルキルチオ基(シクロペンチルチオ、シクロヘキシルチオ等)、アリールチオ基(フェニルチオ、ナフチルチオ等)、ヘテロアリールチオ基(芳香族ヘテロ環チオ基)が挙げられる。)、
-SO2R23(例えば、アルキルスルホニル基(メチルスルホニル、エチルスルホニル、ブチルスルホニル、シクロヘキシルスルホニル、2-エチルヘキシルスルホニル等)、アリールスルホニル(フェニルスルホニル、ナフチルスルホニル、2-ピリジルスルホニル等)が挙げられる。)、
-OSO2R24(メタンスルホニルオキシ等のアルキルスルホニルオキシ基が挙げられる。)、
-NHSO2R25(メチルスルホニルアミノ、オクチルスルホニルアミノ、2-エチルヘキシルスルホニルアミノ、トリフルオロメチルスルホニルアミノ等のスルホニルアミド基が挙げられる。)、
-SO2NR26R27(アミノスルホニル、メチルアミノスルホニル、ジメチルアミノスルホニル、ブチルアミノスルホニル、シクロヘキシルアミノスルホニル、オクチルアミノスルホニル、フェニルアミノスルホニル、2-ピリジルアミノスルホニル等のスルファモイル基が挙げられる。)、
-P(=O)(OR28)2(ジメトキシホスホリル、ジフェニルホスホリル等のホスホリル基が挙げられる。)、
ハロゲン原子(フッ素原子、塩素原子、臭素原子及びヨウ素原子)、
シアノ基、
ニトロ基。
また、置換基Xは、上記メタロセニル基の他に、前述の消光剤部を有することも好ましい。
上記置換基Xとして採りうるアルキル基、アルケニル基及びアルキニル基は、それぞれ、直鎖、分岐、環状のいずれでもよく、直鎖又は分岐が好ましい。
なお、-COOR12のR12が水素原子である場合(すなわち、カルボキシ基)は、水素原子が解離してもよく(すなわち、カルボネート基)、塩の状態であってもよい。また、-OSO2R24のR24が水素原子である場合(すなわち、スルホ基)は、水素原子が解離してもよく(すなわち、スルホネート基)、塩の状態であってもよい。
また、隣接する置換基同士は互いに結合して環を形成してもよく、形成される環としては脂肪族ヘテロ環又はヘテロアリール環が好ましく、形成される環の大きさは特に制限されないが、5員環又は6員環であることが好ましい。また、形成される環の数は特に限定されず、1個であってもよく、2個以上であってもよい。
なお、本発明においては、一般式(2M)中のLが単結合である場合、A、B又はGに直接結合するシクロペンタジエニル環(一般式(2M)中のR1mを有する環)は、A、B又はGと共役する共役構造に含めない。
Rとして採りうる置換基は、特に制限されず、上記置換基Xと同義である。
Lとして、アルキレン基中に、-CO-、-CS-、-NR-(Rは上述の通り。)、-O-、-S-、-SO2-及び-N=CH-の少なくとも1つを含む連結基を採る場合、-CO-等の基は、アルキレン基中のいずれの位置に組み込まれてもよく、また組み込まれる数も特に制限されない。
Lとして採りうる複素環基としては、特に制限されず、例えば、上記Aとして採りうる複素環基として例示した各基から更に水素原子を1つ除去した基が挙げられる。
このアルキル基は、置換基としてハロゲン原子を有していてもよい。ハロゲン原子で置換されたアルキル基としては、例えば、クロロメチル、ジクロロメチル、トリクロロメチル、ブロモメチル、ジブロモメチル、トリブロモメチル、フルオロメチル、ジフルオロメチル、トリフルオロメチル、2,2,2-トリフルオロエチル、パーフルオロエチル、パーフルオロプロピル、パーフルオロブチル等が挙げられる。
また、R1m等として採りうるアルキル基は、炭素鎖を形成する少なくとも1つのメチレン基が-O-又は-CO-で置換されていてもよい。メチレン基が-O-で置換されたアルキル基としては、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、第二ブトキシ、第三ブトキシ、2-メトキシエトキシ、クロロメチルオキシ、ジクロロメチルオキシ、トリクロロメチルオキシ、ブロモメチルオキシ、ジブロモメチルオキシ、トリブロモメチルオキシ、フルオロメチルオキシ、ジフルオロメチルオキシ、トリフルオロメチルオキシ、2,2,2-トリフルオロエチルオキシ、パーフルオロエチルオキシ、パーフルオロプロピルオキシ、パーフルオロブチルオキシの端部メチレン基が置換されたアルキル基、更には、2-メトキシエチル等の炭素鎖の内部メチレン基が置換されたアルキル基等が挙げられる。メチレン基が-CO-で置換されたアルキル基としては、例えば、アセチル、プロピオニル、モノクロロアセチル、ジクロロアセチル、トリクロロアセチル、トリフルオロアセチル、プロパン-2-オン-1-イル、ブタン-2-オン-1-イル等が挙げられる。
R1及びR2として採りうる置換基としては、特に制限はないが、例えば、上記置換基Xにおけるアルキル基(シクロアルキル基を含む)、アルケニル基、アルキニル基、アリール基、ヘテロ環基(芳香族ヘテロ環基及び脂肪族ヘテロ環基を含む)、アルコキシ基、シクロアルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスホリル基、スルファモイル基、アシル基、アシルオキシ基、アミド基、スルホニルアミド基、カルバモイル基、ウレイド基、アルキルスルホニル基、アリールスルホニル基、アミノ基、アルキルスルホニルオキシ基、シアノ基、ニトロ基、ハロゲン原子、ヒドロキシ基等が挙げられる。
また、R41及びR42も、上記のR1及びR2と同義である。
R1、R2、R41及びR42はさらに置換基を有していてもよい。さらに有していてもよい置換基としては、上記置換基Xが挙げられる。
B1~B4として採りうる炭素原子は、水素原子又は置換基を有する。B1~B4として採りうる炭素原子のうち、置換基を有する炭素原子の数は、特に制限されないが、0、1又は2であることが好ましく、1であることがより好ましい。特に、B1及びB4が炭素原子であって、少なくとも一方が置換基を有することが好ましい。
B1~B4として採りうる炭素原子が有する置換基としては、特に制限されず、R1及びR2として採りうる上記置換基が挙げられる。中でも、好ましくは、アルキル基、アルコキシ基、アルコキシカルボニル基、アリール基、アシル基、アミド基、スルホニルアミド基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、アミノ基、シアノ基、ニトロ基、ハロゲン原子又はヒドロキシ基であり、より好ましくは、アルキル基、アルコキシ基、アルコキシカルボニル基、アリール基、アシル基、アミド基、スルホニルアミド基、カルバモイル基、アミノ基、シアノ基、ニトロ基、ハロゲン原子又はヒドロキシ基である。
また、B5、B6、B7およびB8は、それぞれ、上記B1、B2、B3およびB4と同義である。
B1~B8として採り得る炭素原子が有する置換基は、さらに置換基を有していてもよい。さらに有していてもよい置換基としては、上記置換基Xが挙げられる。
B2、B3、B6及びB7として採りうる炭素原子が有する置換基としては、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アミノ基、シアノ基、ニトロ基又はハロゲン原子がさらに好ましく、いずれか一方の置換基が電子求引性基(例えば、アルコキシカルボニル基、アシル基、シアノ基、ニトロ基又はハロゲン原子)であることが特に好ましい。
上記において、形成される環としてはヘテロ環又はヘテロアリール環が好ましく、形成される環の大きさは特に制限されないが、5員環又は6員環であることが好ましい。また、形成される環の数は特に限定されず、1個であってもよく、2個以上であってもよい。2個以上の環が形成される形態としては、例えば、R1とB2が有する置換基、及び、R2とB3が有する置換基とがそれぞれ結合して2個の環を形成する形態が挙げられる。
また、本発明の波長選択吸収フィルタ中における上記染料A~Dの含有量の合計は、通常は70質量%以下であり、50質量%以下が好ましく、40質量%以下がより好ましい。
本発明の波長選択吸収フィルタ中における染料Aの含有量は、0.01~45質量%が好ましく、0.1~30質量%がより好ましい。
本発明の波長選択吸収フィルタ中における染料Bの含有量は、0.01~45質量%が好ましく、0.1~30質量%がより好ましい。
本発明の波長選択吸収フィルタ中における染料Cの含有量は、0.01~30質量%が好ましく、0.1~25質量%がより好ましい。
本発明の波長選択吸収フィルタ中における染料Dの含有量は、0.01~45質量%が好ましく、0.1~30質量%がより好ましい。
本発明の波長選択吸収フィルタに含まれる樹脂(以下、「マトリックス樹脂」とも称す。)は、上記染料及び後記会合抑制剤を分散(好ましくは溶解)することができ、会合抑制剤による染料の会合を抑制し、耐光性の低下を抑制することができる限り、特に限定されるものではない。外光反射の抑制及び輝度低下の抑制を充足することができ、しかも、表示装置(好ましくは自発光表示装置)の画像本来の色味を優れたレベルで保持することができることが、好ましい。
染料Dとして一般式(1)で表されるスクアリン系色素を含有する場合には、上記マトリックス樹脂は、このスクアリン系色素がより先鋭な吸収を示すことが可能な、低極性マトリックス樹脂であることが好ましい。このことは、染料B又はCの少なくとも1つとして国際公開第2019/189463号記載の一般式(1)で表されるスクアリン系色素を含有する場合においても同様である。上記スクアリン系色素がより先鋭な吸収を示すことにより、反射防止と輝度低下抑制を優れたレベルで両立できる。ここで、低極性とは、下記関係式αで定義されるfd値が0.50以上であることが好ましい。
関係式α:fd=δd/(δd+δp+δh)
関係式αにおいて、δd、δp及びδhは、それぞれ、Hoy法により算出される溶解度パラメータδtに対する、London分散力に対応する項、双極子間力に対応する項、及び、水素結合力に対応する項を示す。具体的な算出方法については、後述の通りである。すなわち、fdはδdとδpとδhの和に対するδdの比率を示す。
fd値を0.50以上とすることにより、より先鋭な吸収波形が得られやすくなる。
また、波長選択吸収フィルタがマトリックス樹脂を2種以上含む場合、fd値は、下記のようにして算出する。
fd=Σ(wi・fdi)
ここで、wiはi番目のマトリックス樹脂の質量分率、fdiはi番目のマトリックス樹脂のfd値を示す。
London分散力に対応する項δdは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy (1985,1989)」欄に記載のAmorphous Polymersについて求められるδdをいうものとし、上記文献の上記の欄の記載に従って算出される。
双極子間力に対応する項δpは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy(1985,1989)」欄に記載のAmorphous Polymersについて求められるδpをいうものとし、上記文献の上記の欄の記載に従って算出される。
水素結合力に対応する項δhは、文献“Properties of Polymers 3rd,ELSEVIER,(1990)”の214~220頁の「2)Method of Hoy(1985,1989)」欄に記載のAmorphous Polymersについて求められるδhをいうものとし、上記文献の上記の欄の記載に従って算出される。
なお、樹脂とは、ポリマーに加えて任意の慣用成分を含んでいてもよい。ただし、上記マトリックス樹脂のfdは、マトリックス樹脂を構成するポリマーについての算出値である。
また、例えば、これらの好ましい樹脂に加えて、後述する伸張性樹脂成分及び剥離性制御樹脂成分等の波長選択吸収フィルタに機能性を付与する樹脂成分を用いることも好ましい。すなわち、本発明においてマトリックス樹脂とは、上述の樹脂の他に、伸張性樹脂成分及び剥離性制御樹脂成分を含む意味で使用する。
上記マトリックス樹脂が、ポリスチレン樹脂を含むことが、色素の吸収波形の先鋭化の点から好ましい。
上記ポリスチレン樹脂に含まれるポリスチレンとしては、スチレン成分を含むポリマーを意味する。ポリスチレンはスチレン成分を50質量%以上含むことが好ましい。本発明の波長選択吸収フィルタは、ポリスチレンを、1種含有してもよいし、2種以上を含有してもよい。ここで、スチレン成分とは、その構造中にスチレン骨格を有する単量体由来の構造単位である。
ポリスチレンは、光弾性係数及び吸湿性を波長選択吸収フィルタとして好ましい範囲の値へ制御する点から、スチレン成分を70質量%以上含むことがより好ましく、85質量%以上含むことがさらに好ましい。また、ポリスチレンはスチレン成分のみから構成されていることも好ましい。
具体的なスチレン化合物として、例えば、スチレン;α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、3,5-ジメチルスチレン、2,4-ジメチルスチレン、o-エチルスチレン、p-エチルスチレン及びtert-ブチルスチレン等のアルキルスチレン;ヒドロキシスチレン、tert-ブトキシスチレン、ビニル安息香酸、o-クロロスチレン及びp-クロロスチレン等のスチレンのベンゼン核に水酸基、アルコキシ基、カルボキシ基及びハロゲン原子などが導入された置換スチレンなどが挙げられる。中でも、入手しやすさ、材料価格などの観点から、上記ポリスチレンは、スチレンの単独重合体(すなわちポリスチレン)が好ましい。
また、上記ポリスチレンは、水素添加されていてもよい(水添ポリスチレンであってもよい)。上記水添ポリスチレンとしては、特に限定されないが、スチレン-ブタジエン-スチレンブロック共重合体(SBS)に水素添加した水添スチレン-ブタジエン-スチレンブロック共重合体(SEBS)、及び、スチレン-イソプレン-スチレンブロック共重合体(SIS)に水素を添加した水添スチレン-イソプレン-スチレンブロック共重合体(SEPS)等の、水素添加されたスチレン-ジエン系共重合体が好ましい。上記水添ポリスチレンは、1種のみを使用してもよいし、2種以上を使用してもよい。
また、上記ポリスチレンは、変性ポリスチレンであってもよい。上記変性ポリスチレンとしては、特に限定されないが、極性基等の反応性基が導入されたポリスチレンが挙げられ、具体的には、マレイン酸変性等の酸変性ポリスチレン及びエポキシ変性ポリスチレンが好ましく挙げられる。
ポリスチレン系樹脂は、アニオン、塊状、懸濁、乳化又は溶液重合方法等の常法により得ることができる。また、ポリスチレンにおいては、共役ジエン及びスチレン単量体のベンゼン環の不飽和二重結合の少なくとも一部が水素添加されていてもよい。水素添加率は核磁気共鳴装置(NMR)によって測定できる。
上記ポリフェニレンエーテル樹脂としては、旭化成(株)製のザイロンS201A、同202A、同S203A(いずれも商品名)等を好ましく用いることができる。また、あらかじめポリスチレン樹脂とポリフェニレンエーテル樹脂を混合した樹脂を用いてもよい。ポリスチレン樹脂とポリフェニレンエーテル樹脂との混合樹脂としては、例えば、旭化成(株)製のザイロン1002H、同1000H、同600H、同500H、同400H、同300H、同200H(いずれも商品名)等を好ましく用いることができる。
本発明の波長選択吸収フィルタにおいて、ポリスチレン樹脂とポリフェニレンエーテル樹脂とを併用する場合、両者の質量比は、ポリスチレン樹脂/ポリフェニレンエーテル樹脂で、99/1~50/50が好ましく、98/2~60/40がより好ましく、95/5~70/30がさらに好ましい。ポリフェニレンエーテル樹脂の配合比率を上記好ましい範囲とすることにより、波長選択吸収フィルタは十分な靱性を有し、また溶液成膜をした場合には溶剤を適度に揮散させることができる。
環状ポリオレフィン樹脂に含まれる環状ポリオレフィンを形成する環状オレフィン化合物としては、炭素-炭素二重結合を含む環構造を持つ化合物であれば特に制限されず、例えば、ノルボルネン化合物、ノルボルネン化合物以外の、単環の環状オレフィン化合物、環状共役ジエン化合物及びビニル脂環式炭化水素化合物等が挙げられる。
環状ポリオレフィンとしては、例えば、(1)ノルボルネン化合物に由来する構造単位を含む重合体、(2)ノルボルネン化合物以外の、単環の環状オレフィン化合物に由来する構造単位を含む重合体、(3)環状共役ジエン化合物に由来する構造単位を含む重合体、(4)ビニル脂環式炭化水素化合物に由来する構造単位を含む重合体、及び、(1)~(4)の各化合物に由来する構造単位を含む重合体の水素化物等が挙げられる。
本発明において、ノルボルネン化合物に由来する構造単位を含む重合体、及び、単環の環状オレフィン化合物に由来する構造単位を含む重合体には、各化合物の開環重合体を含む。
一般式(A-II)及び(A-III)中、R3~R6は、各々独立に、水素原子又は炭素数1~10の炭化水素基を示す。
一般式(A-I)~(A-III)における炭化水素基は、炭素原子と水素原子からなる基であれば特に制限されず、アルキル基、アルケニル基、アルキニル基及びアリール基(芳香族炭化水素基)等が挙げられる。中でも、アルキル基又はアリール基が好ましい。
一般式(A-II)及び(A-III)中、X2及びX3、Y2及びY3は、各々独立に、水素原子、炭素数1~10の炭化水素基、ハロゲン原子、ハロゲン原子で置換された炭素数1~10の炭化水素基、-(CH2)nCOOR11、-(CH2)nOCOR12、-(CH2)nNCO、-(CH2)nNO2、-(CH2)nCN、-(CH2)nCONR13R14、-(CH2)nNR13R14、-(CH2)nOZ若しくは-(CH2)nW、又は、X2とY2若しくはX3とY3が互いに結合して形成する、(-CO)2O若しくは(-CO)2NR15を示す。
ここで、R11~R15は、各々独立に、水素原子又は炭素数1~20の炭化水素基を示し、Zは炭化水素基又はハロゲンで置換された炭化水素基を示し、WはSi(R16)pD(3-p)(R16は炭素数1~10の炭化水素基を示し、Dはハロゲン原子、-OCOR17又は-OR17(R17は炭素数1~10の炭化水素基)を示す。pは0~3の整数である)を示す。nは、0~10の整数であり、0~8が好ましく、0~6がより好ましい。
X2及びX3は、それぞれ、水素原子、-CH3又は-C2H5が好ましく、透湿度の点で、水素原子がより好ましい。
Y2及びY3は、それぞれ、水素原子、ハロゲン原子(特に塩素原子)又は-(CH2)nCOOR11(特に-COOCH3)が好ましく、透湿度の点で、水素原子がより好ましい。
その他の基は、適宜に選択される。
ここで、R11~R15は、各々独立に、水素原子又は炭素数1~20の炭化水素基を示し、Zは炭化水素基又はハロゲンで置換された炭化水素基を示し、WはSi(R16)pD(3-p)(R16は炭素数1~10の炭化水素基を示し、Dはハロゲン原子、-OCOR17又は-OR17(R17は炭素数1~10の炭化水素基)を示す。pは0~3の整数である)を示す。nは0~10の整数である。
ノルボルネン化合物の重合体としては、ノルボルネン化合物(例えば、ノルボルネンの多環状不飽和化合物)同士を付加重合することによって得られる。
このようなノルボルネン化合物の付加(共)重合体としては、三井化学社よりアペルの商品名で発売されており、ガラス転移温度(Tg)が互いに異なる、APL8008T(Tg70℃)、APL6011T(Tg105℃)、APL6013T(Tg125℃)、及び、APL6015T(Tg145℃)等が挙げられる。また、ポリプラスチック社より、TOPAS8007、同6013、同6015等のペレットが市販されている。さらに、Ferrania社よりAppear3000が市販されている。
本発明の波長選択吸収フィルタ中の上記マトリックス樹脂の含有量は、通常は99.90質量%以下であり、99.85質量%以下が好ましい。
本発明の波長選択吸収フィルタが含有する環状ポリオレフィンは2種以上であってもよく、組成比及び分子量の少なくとも一方が異なるポリマー同士を併用してもよい。この場合、各ポリマーの合計含有量が上記範囲内となる。
本発明の波長選択吸収フィルタは、樹脂成分として伸長性を示す成分(伸長性樹脂成分とも称す。)を適宜選んで含むことができる。具体的には、アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)、スチレン-ブタジエン樹脂(SB樹脂)、イソプレン樹脂、ブタジエン樹脂、ポリエーテル-ウレタン樹脂及びシリコーン樹脂等を挙げることができる。また、これらの樹脂をさらに、適宜水素添加してもよい。
上記伸長性樹脂成分としては、ABS樹脂又はSB樹脂を用いることが好ましく、SB樹脂を用いることがより好ましい。
本発明の波長選択吸収フィルタは、後述する本発明の波長選択吸収フィルタの製造方法のうち、剥離フィルムから波長選択吸収フィルタの剥離を行う工程を含む方法により作製する場合には、樹脂成分として剥離性を制御する成分(剥離性制御樹脂成分)を含むことができ、好ましい。剥離フィルムからの波長選択吸収フィルタの剥離性を制御することで、剥離後の波長選択吸収フィルタに剥ぎとった跡が付くことを防ぐことができ、また、剥離工程における種々の加工速度への対応が可能となる。これらの結果、波長選択吸収フィルタの品質及び生産性向上に好ましい効果を得ることができる。
また、剥離フィルムとしてポリエステル系ポリマーフィルムを用いる場合、剥離性制御樹脂成分として、例えばスチレン系エラストマーも好適に用いられる。
上記ポリエステル系添加剤の質量平均分子量が上記好ましい下限値以上であると、脆性、湿熱耐久性の観点で好ましく、上記好ましい上限値以下であると、樹脂との相溶性の観点で好ましい。
上記ポリエステル系添加剤の質量平均分子量は、以下の条件で測定した標準ポリスチレン換算の質量平均分子量(Mw)の値である。分子量分布(Mw/Mn)についても、同じ条件により測定することができる。なお、Mnは標準ポリスチレン換算の数平均分子量である。
GPC:ゲル浸透クロマトグラフ装置(東ソー(株)製HLC-8220GPC、
カラム;東ソー(株)製ガードカラムHXL-H、TSK gel G7000HXL、TSK gel GMHXL2本、TSK gel G2000HXLを順次連結、
溶離液;テトラヒドロフラン、
流速;1mL/min、
サンプル濃度;0.7~0.8質量%、
サンプル注入量;70μL、
測定温度;40℃、
検出器;示差屈折(RI)計(40℃)、
標準物質;東ソー(株)製TSKスタンダードポリスチレン)
このジカルボン酸としては、脂肪族ジカルボン酸及び芳香族ジカルボン酸等が挙げられ、芳香族ジカルボン酸、又は、芳香族ジカルボン酸と脂肪族ジカルボン酸の混合物を好ましく用いることができる。
脂肪族ジオールの中でも、炭素数2~4の脂肪族ジオールが好ましく、炭素数2~3の脂肪族ジオールがより好ましい。
脂肪族ジオールとしては、例えば、エチレングリコール、ジエチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,3-ブチレングリコール及び1,4-ブチレングリコールなどが挙げることができ、これらを単独又は二種類以上を併用して用いることができる。
また、ポリスチレン系エラストマーは水素添加物であると、熱に対する安定性が向上し、分解又は重合等の変質が起こりにくい。さらに、溶剤への溶解性の観点からもより好ましい。
ポリスチレン系エラストマーの不飽和二重結合量としては、剥離性の観点から、ポリスチレン系エラストマー1gあたり、15mmol未満であることが好ましく、5mmol未満であることがより好ましく、0.5mmol未満であることがさらに好ましい。なお、ここでいう不飽和二重結合量は、スチレン由来のベンゼン環内の不飽和二重結合の量を含まない。不飽和二重結合量は、NMR(核磁気共鳴)測定により算出することができる。
本発明の波長選択フィルタは、極性基を有する化合物(本発明において「会合抑制剤」とも称す。)を含有する。
本発明においては、上記会合抑制剤は、カルボン酸エステル結合、カルボン酸アミド結合、スルホン酸アミド結合、ウレタン結合及びスルホニル結合(>S(=O)2)の少なくともいずれか1つの極性基を有する。これらの極性基は2価の置換基(結合)として化合物中に含まれる。
上記会合抑制剤は、上述の染料とは異なり、本発明の波長選択吸収フィルタに含有された状態で、実質的に色を呈しない化合物である。
また、上記会合抑制剤は、本発明の波長選択吸収フィルタ中において、樹脂中に分散又は溶解する染料A又はDについて、染料の分子同士の会合を抑制する機能を発現する化合物であり、上述の樹脂とは異なる。すなわち、上記会合抑制剤の分子量は、1000以下であり、100~1000が好ましく、200~1000がより好ましく、200~900がさらに好ましい。
また、上記会合抑制剤は、後述する褪色防止剤としての機能を示す化合物ではない。
また、上記会合抑制剤は、フィルタ内における均一分散の観点から、フッ素化アルキル基を有しないことが好ましい。
上記会合抑制剤中に含有される極性基の種類は、特に制限はなく、1種であっても2種以上であってもよいが、1種又は2種であることが好ましく、1種であることがより好ましい。なお、極性基の種類は、カルボン酸エステル結合に分類される極性基を1種類、カルボン酸アミド結合に分類される極性基を1種類、スルホン酸アミド結合に分類される極性基を1種類、ウレタン結合に分類される極性基を1種類、スルホニル結合に分類される極性基を1種類としてそれぞれ数える。
上記会合抑制剤は、カルボン酸エステル結合又はカルボン酸アミド結合を有することが好ましい。
下記一般式(2)又は(3)で表される化合物は、カルボン酸エステル結合又はカルボン酸アミド結合の少なくとも一つが環構造に直接結合した構造を有する化合物である。ただし、一般式(18)で表される化合物にも該当する場合には、一般式(18)で表される化合物に分類する。
後記一般式(4)~(12)のいずれかで表される化合物は、カルボン酸エステル結合、カルボン酸アミド結合又はウレタン結合の少なくともいずれか1つを有する化合物である。ただし、一般式(2)又は(3)で表される化合物にも該当する場合には、一般式(2)又は(3)で表される化合物に分類する。
後記一般式(13)で表される化合物は、スルホン酸アミド結合を有する化合物である。
後記一般式(14)で表される化合物は、スルホニル結合を有する化合物である。
後記一般式(18)で表される化合物は、カルボン酸アミド結合を有する化合物である。
以降、各一般式について順に説明する。
Zを環構成原子とする5または6員環は置換基を有していてもよい。Zを環構成原子とする5または6員環が有していてもよい置換基としては、特に制限されないが、例えば、オキソ基(=O)、チオキソ基(=S)が挙げられる。
Zを環構成原子とする5または6員環が複数の置換基を有する場合、隣接する置換基が互いに結合して環を形成していてもよい。この隣接する置換基が互いに結合して形成される環は、芳香族環であっても非芳香族環であってもよい。
Zを環構成原子とする5または6員環の例としては、テトラヒドロフラン、テトラヒドロピラン、テトラヒドロチオフェン、チアン、ピロリジン、ピペリジンなどを挙げることができる。また、Zを環構成原子とする5または6員環が縮環している場合、この縮環構造の例としては、インドリン、イソインドリン、クロマン、イソクロマンなどを挙げることができる。
また、Zを環構成原子とする5または6員環は、ラクトン構造またはラクタム構造、すなわち、Zに結合する環構成炭素原子がオキソ基(=O)で置換されている、環状エステルまたは環状アミド構造であってもよい。このような環状エステルまたは環状アミド構造の例としては、テトラヒドロ-2-フラノン(5-ペンタノリドとも称す。)、テトラヒドロ-2-ピロン(6-ヘキサノリドとも称す。)等のラクトン、4-ブタンラクタム(2-ピロリドンとも称す。)、5-ペンタンラクタム(2-ピペリドンとも称す。)等のラクタムを挙げることができる。
R25として採り得るアルキル基は、鎖状、分岐状および環状のいずれであってもよく、炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。
R25として採り得るアルキル基としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、t-ブチル、n-ペンチル、t-アミル、n-ヘキシル、n-オクチル、デシル、ドデシル、エイコシル、2-エチルヘキシル、シクロペンチル、シクロヘキシル、シクロヘプチル、2,6-ジメチルシクロヘキシル、4-t-ブチルシクロヘキシル、シクロペンチル、1-アダマンチル、2-アダマンチル、ビシクロ[2.2.2]オクタン-3-イルなどを挙げることができる。
Y21又はY22として採り得るアシルオキシ基としては、炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。例えば、アセトキシ、エチルカルボニルオキシ、プロピルカルボニルオキシ、n-ブチルカルボニルオキシ、iso-ブチルカルボニルオキシ、t-ブチルカルボニルオキシ、sec-ブチルカルボニルオキシ、n-ペンチルカルボニルオキシ、t-アミルカルボニルオキシ、n-ヘキシルカルボニルオキシ、シクロヘキシルカルボニルオキシ、1-エチルペンチルカルボニルオキシ、n-ヘプチルカルボニルオキシ、n-ノニルカルボニルオキシ、n-ウンデシルカルボニルオキシ、ベンジルカルボニルオキシ、1-ナフタレンカルボニルオキシ、2-ナフタレンカルボニルオキシ、1-アダマンタンカルボニルオキシなどを挙げることができる。
Y21又はY22として採り得るアルコキシカルボニル基としては、炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。例えば、メトキシカルボニル、エトキシカルボニル、n-プロピルオキシカルボニル、イソプロピルオキシカルボニル、n-ブトキシカルボニル、t-ブトキシカルボニル、iso-ブチルオキシカルボニル、sec-ブチルオキシカルボニル、n-ペンチルオキシカルボニル、t-アミルオキシカルボニル、n-ヘキシルオキシカルボニル、シクロヘキシルオキシカルボニル、2-エチルヘキシルオキシカルボニル、1-エチルプロピルオキシカルボニル、n-オクチルオキシカルボニル、3,7-ジメチル-3-オクチルオキシカルボニル、3,5,5-トリメチルヘキシルオキシカルボニル、4-t-ブチルシクロヘキシルオキシカルボニル、2,4-ジメチルペンチル-3-オキシカルボニル、1-アダマンタンオキシカルボニル、2-アダマンタンオキシカルボニル、ジシクロペンタジエニルオキシカルボニル、n-デシルオキシカルボニル、n-ドデシルオキシカルボニル、n-テトラデシルオキシカルボニル、n-ヘキサデシルオキシカルボニルなどを挙げることができる。
Y21又はY22として採り得るアミド基(アシルアミノ基)としては、炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。例えば、アセタミド、エチルカルボキサミド、n-プロピルカルボキサミド、イソプロピルカルボキサミド、n-ブチルカルボキサミド、t-ブチルカルボキサミド、iso-ブチルカルボキサミド、sec-ブチルカルボキサミド、n-ペンチルカルボキサミド、t-アミルカルボキサミド、n-ヘキシルカルボキサミド、シクロヘキシルカルボキサミド、1-エチルペンチルカルボキサミド、1-エチルプロピルカルボキサミド、n-ヘプチルカルボキサミド、n-オクチルカルボキサミド、1-アダマンタンカルボキサミド、2-アダマンタンカルボキサミド、n-ノニルカルボキサミド、n-ドデシルカルボキサミド、n-ペンタカルボキサミド、n-ヘキサデシルカルボキサミドなどを挙げることができる。
Y21又はY22として採り得るカルバモイル基としては、炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。例えば、メチルカルバモイル、ジメチルカルバモイル、エチルカルバモイル、ジエチルカルバモイル、n-プロピルカルバモイル、イソプロピルカルバモイル、n-ブチルカルバモイル、t-ブチルカルバモイル、iso-ブチルカルバモイル、sec-ブチルカルバモイル、n-ペンチルカルバモイル、t-アミルカルバモイル、n-ヘキシルカルバモイル、シクロヘキシルカルバモイル、2-エチルヘキシルカルバモイル、2-エチルブチルカルバモイル、t-オクチルカルバモイル、n-ヘプチルカルバモイル、n-オクチルカルバモイル、1-アダマンタンカルバモイル、2-アダマンタンカルバモイル、n-デシルカルバモイル、n-ドデシルカルバモイル、n-テトラデシルカルバモイル、n-ヘキサデシルカルバモイルなどを挙げることができる。
Y31~Y70として採り得るアシルオキシ基、アルコキシカルボニル基、アミド基及びカルバモイル基としては、上記一般式(2)又は(3)におけるY21又はY22として採り得るアシルオキシ基、アルコキシカルボニル基、アミド基及びカルバモイル基の記載をそれぞれ適用することができる。
Y31~Y70として採り得るカルバモイルオキシ基におけるカルバモイル基部分としては、上記一般式(2)又は(3)におけるY21又はY22として採り得るカルバモイル基の記載を適用することができる。
V31~V43として採り得る脂肪族基の炭素数は、1~20が好ましく、1~16がより好ましく、1~12がさらに好ましい。
ここで、脂肪族基とは、好ましくは脂肪族炭化水素基であり、鎖状、分岐状および環状のいずれであってもよい。より好ましくは、アルキル基、アルケニル基またはアルキニル基である。
アルキル基としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、t-ブチル、n-ペンチル、t-アミル、n-ヘキシル、n-オクチル、デシル、ドデシル、エイコシル、2-エチルヘキシル、シクロペンチル、シクロヘキシル、シクロヘプチル、2,6-ジメチルシクロヘキシル、4-t-ブチルシクロヘキシル、シクロペンチル、1-アダマンチル、2-アダマンチル、ビシクロ[2.2.2]オクタン-3-イルなどが挙げられ、アルケニル基としては、例えば、ビニル、アリル、プレニル、ゲラニル、オレイル、2-シクロペンテン-1-イル、2-シクロヘキセン-1-イルなどが挙げられ、アルキニル基としては、例えば、エチニル、プロパルギルなどを挙げることができる。
L31~L64及びL66~L80として採り得る上記2価の飽和の連結基の好ましい例としては、アルキレン基(例えば、メチレン、エチレン、プロピレン、トリメチレン、テトラメチレン、ペンタメチレン、ヘキサメチレン、メチルエチレン、エチルエチレンなど。ただしシクロアルキレン基を除く。)、環式の2価の基(例えば、cis-1,4-シクロヘキシレン、trans-1,4-シクロヘキシレン、1,3-シクロペンチリデンなど)、エーテル結合(-O-)、チオエーテル結合(-S-)、エステル結合(-C(=O)O-又は-CO(=O)-)、アミド結合(-C(=O)NH-又は-NHC(=O)-)、スルフィニル結合(-S(=O)-)、スルホニル結合(-S(=O)2-)、スルホンアミド結合(-NHS(=O)2-又は-S(=O)2NH-)、ウレイレン結合(-NHC(=O)NH-)又はチオウレイレン結合(-NHS(=O)NH-)などを挙げることができる。これらの2価の基の2つ以上が互いに結合して二価の複合基を形成してもよく、複合置換基の例としては、-(CH2)2O(CH2)2-、-(CH2)2O(CH2)2O(CH2)-、-(CH2)2S(CH2)2-又は-(CH2)2O2C(CH2)2-などを挙げることができる。
なお、本発明において、具体例として記載される化学構造中において、Meはメチル基を示し、t-Buはtert-ブチル基を示し、Priはisoプロピル基を示し、n-はノルマルを示す。
R1~R5として採り得るアリール基の炭素数は、6~30が好ましく、6~24がより好ましい。例えば、フェニル、ビフェニル、テルフェニル、ナフチル、ビナフチル、トリフェニルフェニルが挙げられる。
R1~R5として採り得るアルキル基およびアリール基は置換基を有していてもよい。有していてもよい置換基としては、ハロゲン原子(フッ素原子、塩素原子等)、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アリールカルボニル基、アルコキシカルボニル基、スルホニル基、スルホンアミド基、アミノ基、ヒドロキシ基又はシアノ基が好ましく挙げられる。また、これらの置換基を2つ以上組合わせてなる置換基も好ましく挙げられる。
R1~R5として採り得るアルキル基およびアリール基が有していてもよい置換基をとしては、アルキル基、アリール基、アルコキシ基、スルホン基又はスルホンアミド基がより好ましい。
R4およびR5の炭素原子数の合計は10以上であり、10~40が好ましく、12~30がより好ましい。
R1~R3として採り得るアリール基は、炭素数は6~36が好ましく、6~24がより好ましい。なかでも、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
なお、R1~R3として採り得るアルキル基およびアリール基が有していてもよい置換基は、さらに置換基で置換されていてもよい。さらに有していてもよい置換基としては、上記のR1~R3として採り得るアルキル基およびアリール基が有していてもよい置換基の記載を好ましく適用することができ、例えばアルキル基が挙げられる。
環状構造としては、飽和もしくは不飽和の脂肪族炭化水素環、及び、芳香族炭化水素環のいずれでもよく、芳香族炭化水素環であることが好ましい。
化合物中における環状構造の数は特に制限されず、例えば、1~7個が好ましく、1~5個がより好ましく、2又は3個がさらに好ましい。
また、一般式(18)で表される化合物は、長鎖アルキル基を有しないことが耐光性をより向上させる観点から好ましい。ここで長鎖アルキル基とは、アルキル基を構成する炭素-炭素結合のうち最長となる結合を構成する炭素原子の数が7以上である基を意味する。
ベンゼン環上にアルコキシカルボニル基を有する化合物としては、なかでも、フタル酸エステル化合物又はトリメリット酸エステル化合物が好ましい。
フタル酸エステル化合物としては、フタル酸(オルト、メタ、パラのいずれの異性体でもよい。)と炭素数4~10のアルコールとのエステル化合物が好ましい。具体的には、フタル酸ジシクロヘキシル、フタル酸ジフェニル、フタル酸ジトリル等が挙げられる。なかでもフタル酸ジシクロヘキシル又はフタル酸ジフェニルが好ましい。
トリメリット酸エステル化合物としては、トリメリット酸と炭素数4~10のアルコールとのエステル化合物が好ましい。具体的には、トリメリット酸トリブチル、トリメリット酸トリ(2-エチルヘキシル)、トリメリット酸トリノルマルオクチル、トリメリット酸トリノルマルデシル、トリメリット酸トリイソデシルが挙げられる。なかでもトリメリット酸トリブチル、トリメリット酸トリ(2-エチルヘキシル)又はトリメリット酸トリイソデシルが好ましい。
上記会合抑制剤は、本発明の波長選択吸収フィルタ中において、染料A及び染料Cの合計含有量100質量部に対して、10~1000質量部の割合で含まれることが好ましく、30~700質量部の割合で含まれることがより好ましく、50~500質量部の割合で含まれることがさらに好ましい。
本発明の波長選択吸収フィルタは、前述の染料とマトリックス樹脂と会合抑制剤に加え、染料の褪色防止剤、マット剤及びレベリング(界面活性剤)剤等を含んでもよい。
本発明の波長選択吸収フィルタは、上記染料A及びDの少なくとも1種を含む染料の褪色を防止するため、染料の褪色防止剤(単に、褪色防止剤とも称す。)を含有してもよい。
上記褪色防止剤としては、国際公開第2015/005398号の段落[0143]~[0165]に記載の酸化防止剤、同[0166]~[0199]に記載のラジカル捕捉剤、及び同[0205]~[0206]に記載の劣化防止剤等、通常用いられる褪色防止剤を特に限定することなく用いることができる。
褪色防止剤を上記好ましい範囲内で含有することにより、波長選択吸収フィルタの変色等の副作用を起こすことなく、染料(色素)の耐光性を向上させることができる。
本発明の波長選択吸収フィルタの表面には、滑り性付与及びブロッキング防止のために微粒子(マット剤とも称す。)を添加することが好ましい。マット剤としては、国際公開第2019/189463号の[0253]~[0255]に記載のマット剤の記載を特に限定することなく用いることができる。なお、国際公開第2019/189463号における「本発明のフィルタ」については、「本発明の波長選択吸収フィルタ」に読み替えるものとする。
ただし、本発明の波長選択吸収フィルタがガスバリア層を有する場合においては、波長選択吸収フィルタの表面のうちガスバリア層と接する面には、本発明の効果を損なわない範囲で上記マット剤微粒子を付与することが好ましい。
本発明の波長選択吸収フィルタには、レベリング剤(界面活性剤)を適宜混合することができる。レベリング剤としては、常用の化合物を使用することができ、特に含フッ素界面活性剤が好ましい。具体的には、例えば、特開2001-330725号公報明細書中の段落番号[0028]~[0056]記載の化合物が挙げられる。
本発明の波長選択吸収フィルタ中のレベリング剤の含有量は目的に応じて適宜に調整される。
本発明の波長選択吸収フィルタは、常法により、溶液製膜法、溶融押出し法、又は、基材フィルム(剥離フィルム)上に任意の方法でコーティング層を形成する方法(コーティング法)で作製することができ、適宜延伸を組み合わせることもできる。
溶液製膜法及び溶融押出し法については、国際公開第2019/189463号の[0259]~[0265]に記載の溶液製膜法及び溶融押出し法を特に限定することなく用いることができる。なお、国際公開第2019/189463号における「本発明のフィルタ」又は「フィルタ」は本発明の波長選択吸収フィルタとして読み替えるものとする。
本発明の波長選択吸収フィルタは、好ましくはコーティング法により作製される。
コーティング法では、本発明の波長選択吸収フィルタの材料の溶液を、濃縮工程又はろ過工程などを適宜実施した後に、剥離フィルム上に塗布し、乾燥させ、コーティング層を形成する。剥離フィルム表面には、コーティング層との接着性を制御するため、適宜、離型剤等を予め塗布しておいてもよい。コーティング層は、後工程で接着層を介して他の部材と積層させた後、剥離フィルムを剥離して用いることができる。接着層を構成する接着剤については、任意の接着剤を適宜使用することができる。なお、剥離フィルム上に、本発明の波長選択吸収フィルタの材料の溶液を塗布した状態又はコーティング層が積層された状態で、適宜剥離フィルムごと延伸することができる。
波長選択吸収フィルタ材料に上記染料及び上記会合抑制剤を添加するタイミングは、製膜される時点で添加されていれば特に限定されない。例えば、上記マトリックス樹脂の合成時点で添加してもよいし、波長選択吸収フィルタ材料のコーティング液調製時に波長選択吸収フィルタ材料と混合してもよい。その他、レベリング剤等の波長選択吸収フィルタ中に含有していてもよいその他の成分についても同様である。
波長選択吸収フィルタを、コーティング法等で形成させるために用いられる剥離フィルムは、膜厚が5~100μmであることが好ましく、10~75μmがより好ましく、15~55μmがさらに好ましい。膜厚が上記好ましい下限値以上であると、十分な機械強度を確保しやすく、カール、シワ、座屈等の故障が生じにくい。また、膜厚が上記好ましい上限値以下であると、本発明の波長選択吸収フィルタと剥離フィルムとの複層フィルムを、例えば長尺のロール形態で保管する場合に、複層フィルムにかかる面圧を適正な範囲に調整しやすく、接着の故障が生じにくい。
剥離フィルムの波長選択吸収フィルタを形成する側の表面エネルギーは、41.0~48.0mN/mであることが好ましく、42.0~48.0mN/mであることがより好ましい。表面エネルギーが上記好ましい下限値以上であると、波長選択吸収フィルタの厚みの均一性を高められ、上記好ましい上限値以下であると、波長選択吸収フィルタを剥離フィルムとの剥離力を適切な範囲に制御しやすい。
本発明の波長選択吸収フィルタを、コーティング法で形成させる場合、波長選択吸収フィルタと剥離フィルムとの間の剥離力は、波長選択吸収フィルタの材料、剥離フィルムの材料、波長選択吸収フィルタの内部歪み等を調整して制御することができる。この剥離力は、例えば、剥離フィルムを90°方向に剥がす試験で測定することができ、300mm/分の速度で測定したときの剥離力が、0.001~5N/25mmが好ましく、0.01~3N/25mmがより好ましく、0.05~1N/25mmがさらに好ましい。上記好ましい下限値以上であれば、剥離フィルムの剥離工程以外での剥離を防ぐことができ、上記好ましい上限値以下であれば、剥離工程における剥離不良(例えば、ジッピング及び波長選択吸収フィルタの割れ)を防ぐことができる。
本発明の波長選択吸収フィルタの膜厚は、特に制限されないが、1~18μmが好ましく、1~12μmがより好ましく、1~8μmがさらに好ましい。上記好ましい上限値以下であれば、薄いフィルムに高濃度で染料を添加することにより、染料(色素)が発する蛍光による偏光度の低下を抑えることができる。また、消光剤及び褪色防止剤の効果も発現しやすい。一方、上記好ましい下限値以上であると、面内の吸光度の均一度を維持しやすくなる。
本発明において膜厚が1~18μmであるとは、波長選択吸収フィルタの厚さを、どの部位で図っても1~18μmの範囲内にあることを意味する。このことは、膜厚1~12μm、1~8μmについても同様である。膜厚は、アンリツ(株)社製電子マイクロメーターにより測定することができる。
本発明の波長選択吸収フィルタの波長390~440nmにおける最小透過率は0%以上98%以下が好ましく、0%以上90%以下がより好ましく、0%以上80%以下がさらに好ましい。
また、本発明の波長選択吸収フィルタの波長480~520nmにおける最小透過率は5%以上98%以下が好ましく、10%以上95%以下がより好ましく、20%以上90%以下がさらに好ましい。
また、本発明の波長選択吸収フィルタの波長580~620nmにおける最小透過率は0%以上99%以下が好ましく、0%以上98%以下がより好ましく、0%以上95%以下がさらに好ましい。
また、本発明の波長選択吸収フィルタの波長680~780nmにおける最小透過率は0%以上95%以下が好ましく、0%以上90%以下がより好ましく、0%以上80%以下がさらに好ましい。
透過率を上記範囲に調節した本発明の波長選択吸収フィルタを表示装置(好ましくは自発光表示装置)に組み込むことにより、より高輝度で、外光反射もより抑制、反射光の色差が小さい表示性能が得られる。
本発明の波長選択吸収フィルタの透過率は、染料の種類及び添加量、会合抑制剤の種類及び添加量、樹脂種等により調整することができる。
本発明の波長選択吸収フィルタには任意のグロー放電処理、コロナ放電処理、又は、アルカリ鹸化処理などにより親水化処理を施してもよく、コロナ放電処理が好ましく用いられる。特開平6-94915号公報、又は同6-118232号公報などに開示されている方法などを適用することも好ましい。
好ましくは、後述の表示装置における粘着剤層の記載を適用することができる。
本発明の波長選択吸収フィルタは、本発明の波長選択吸収フィルタの少なくとも片面に直接配されたガスバリア層を有し、かつ、このガスバリア層が、結晶性樹脂を含有し、層の厚みが0.1μm~10μmであって、層の酸素透過度が60cc/m2・day・atm以下であることが、好ましい。
上記ガスバリア層において、上記「結晶性樹脂」は、温度を上げた際に結晶から液体に相転移する融点が存在する樹脂であって、上記ガスバリア層に、酸素ガスに係るガスバリア性を付与できるものである。
上記ガスバリア層に含まれる結晶性樹脂としては、ガスバリア性を有する結晶性樹脂であって、ガスバリア層に所望の酸素透過度を付与できる限り、特に制限することなく用いることができる。
上記結晶性樹脂としては、例えば、ポリビニルアルコール及びポリ塩化ビニリデンを挙げることができ、結晶部がガスの透過を効果的に抑制することができる点から、ポリビニルアルコールが好ましい。
上記ポリビニルアルコールは、変性されていてもよく、変性されていなくてもよい。変性ポリビニルアルコールとしては、アセトアセチル基、カルボキシル等の基を導入した変性ポリビニルアルコールが挙げられる。
上記ポリビニルアルコールのけん化度は、酸素ガスバリア性をより高める観点から、80.0mol%以上が好ましく、90.0mol%以上がより好ましく、97.0mol%以上がさらに好ましく、98.0mol%以上が特に好ましい。上限値に特に制限はないが、99.99mol%以下が実際的である。上記ポリビニルアルコールのけん化度は、JIS K 6726 1994に記載の方法に基づき算出される値である。
上記ガスバリア層は、本発明の効果を損なわない範囲で、通常ガスバリア層に含有される任意の成分を含んでいてもよい。例えば、上記結晶性樹脂に加え、非晶性樹脂材料、ゾルゲル材料などの有機-無機ハイブリッド系材料、SiO2、SiOx、SiON、SiNx及びAl2O3などの無機系材料を含有していてもよい。
また、上記ガスバリア層は、本発明の効果を損なわない範囲で、製造工程に起因した水及び有機溶媒等の溶媒を含有していてもよい。
上記ガスバリア層中の結晶性樹脂の含有量は、例えば、ガスバリア層の全質量100質量%中、90質量%以上が好ましく、95質量%以上がより好ましい。上限値に特に制限はないが、100質量%とすることもできる。
なお、ガスバリア層の酸素透過度は、JIS K 7126-2 2006に基づくガス透過度試験方法に基づいて測定した値である。測定装置としては、例えば、MOCON社製の酸素透過率測定器、OX-TRAN2/21(商品名)を用いることができる。なお、測定条件は、温度25℃、相対湿度50%とする。
酸素透過度は、SI単位として、(fm)/(s・Pa)を用いることができる。(1fm)/(s・Pa)=8.752(cc)/(m2・day・atm)で換算することが可能である。fmはフェムトメートルと読み、1fm=10-15mを表わす。
上記ガスバリア層の厚みは、後述の実施例に記載の方法により測定される。
上記ガスバリア層に含まれる結晶性樹脂の結晶化度は、J. Appl. Pol. Sci., 81, 762(2001)に記載の方法に基づき、以下の方法により測定、算出される値である。
DSC(示唆走査熱量計)を用い、ガスバリア層から剥離した試料について、20℃から260℃の範囲にかけて10℃/minで昇温し、融解熱1を測定する。また、完全結晶の融解熱2として、J. Appl. Pol. Sci., 81, 762(2001)に記載の値を用いる。得られた融解熱1及び融解熱2を用い、以下の式により結晶化度を算出する。
[結晶化度(%)]=([融解熱1]/[融解熱2])×100
具体的には、上記結晶化度は、後述の実施例に記載の方法により測定、算出される値である。なお、融解熱1と融解熱2とは同じ単位であればよく、通常、Jg-1である。
ガスバリア層を形成する方法は特に制限されないが、常法により、スピン塗布及びスリット塗布等のキャスト法に作成する方法が挙げられる。また、市販の樹脂製ガスバリアフィルム又はあらかじめ作製しておいた樹脂性ガスバリアフィルムを、本発明の波長選択吸収フィルタに貼り合せる方法などを挙げることができる。
本発明の波長選択吸収フィルタは、上記ガスバリア層以外に、本発明の効果を損なわない範囲で、任意の光学フィルムを適宜有していてもよい。
上記任意の光学フィルムについては、光学特性及び材料のいずれについても特に制限はないが、セルロースエステル樹脂、アクリル樹脂、環状オレフィン樹脂及びポリエチレンテレフタレート樹脂の少なくともいずれかを含む(あるいは主成分とする)フィルムを好ましく用いることができる。なお、光学的に等方性のフィルムを用いても、光学的に異方性の位相差フィルムを用いてもよい。
上記任意の光学フィルムについて、セルロースエステル樹脂を含むものとしては、例えばフジタックTD80UL(富士フイルム(株)製)などを利用することができる。
上記任意の光学フィルムについて、アクリル樹脂を含むものとしては、特許第4570042号公報に記載のスチレン系樹脂を含有する(メタ)アクリル樹脂を含む光学フィルム、特許第5041532号公報に記載のグルタルイミド環構造を主鎖に有する(メタ)アクリル樹脂を含む光学フィルム、特開2009-122664号公報に記載のラクトン環構造を有する(メタ)アクリル系樹脂を含む光学フィルム、特開2009-139754号公報に記載のグルタル酸無水物単位を有する(メタ)アクリル系樹脂を含む光学フィルムを利用することができる。
また、上記任意の光学フィルムについて、環状オレフィン樹脂を含むものとしては、特開2009-237376号公報の段落[0029]以降に記載の環状オレフィン系樹脂フィルム、特許第4881827号公報、特開2008-063536号公報に記載のRthを低減する添加剤を含有する環状オレフィン樹脂フィルムを利用することができる。
また、上記任意の光学フィルムは、紫外線吸収剤を含有していてもよい。紫外線吸収剤としては、特に制限することなく常用の化合物を使用できる。
上記紫外線吸収層中の紫外線吸収剤の含有量は目的に応じて適宜に調整される。
本発明の波長選択吸収フィルタが、本発明の波長選択吸収フィルタに加え、上述のガスバリア層又は任意の光学フィルムを有する場合、これらの波長選択吸収フィルタと、ガスバリア層及び/又は任意の光学フィルムからなる積層体は、上述の波長選択吸収フィルタの製造方法及びガスバリア層の製造方法を用いて、作製することができる。
例えば、上述の製造方法により作製した波長選択吸収フィルタ上に、直接、上述のガスバリア層を作製する方法が挙げられる。この場合、波長選択吸収フィルタのうち、ガスバリア層を設ける面には、コロナ処理を施しておくことも好ましい。
また、上記任意の光学フィルムを設ける場合には、粘着剤層を介して貼り合わせることも好ましい。例えば、波長選択吸収フィルタ上にガスバリア層を設けた後、さらに粘着剤層を介して紫外線吸収剤を含有する光学フィルムを貼り合わせることも好ましい。
本発明の表示装置は、本発明の波長選択吸収フィルタを含む。
本発明の表示装置としては、本発明の波長選択吸収フィルタを、外光反射防止機能を奏するような位置に含む構成である限り(上記ガスバリア層を含む場合には、さらに、上記ガスバリア層が少なくとも本発明の波長選択吸収フィルタよりも外光側に位置するような構成で含む限り)、その他の構成としては、通常用いられている表示装置の構成を特に制限することなく用いることができる。
表示装置としては、特に制限はされないが、有機発光ダイオード(OLED)表示装置、マイクロ発光ダイオード(マイクロLED)表示装置、ミニ発光ダイオード(ミニLED)表示装置等の、発光ダイオードを発光源として備える自発光型の表示装置(自発光表示装置)が、本発明の波長選択吸収フィルタを含むことにより、本発明の波長選択吸収フィルタが示す優れた耐光性をより効果的に奏することができる観点から好ましい。
上記自発光表示装置の構成例としては、特に制限されないが、例えば、外光に対して反対側から順に、ガラス、TFT(薄膜トランジスタ)を含む層、発光素子、本発明の波長選択吸収フィルタ及び表面フィルムを含む表示装置が挙げられる。
上記自発光表示装置の表示光の光源は、発光ダイオードを発光源として備えるものである限り、青色単色でもよく、青色、緑色及び赤色の三原色を用いてもよい。なかでも、波長域440nm~470nmで発光する青色光源、波長域520nm~560nmで発光する緑色光源及び波長域620nm~660nmで発光する赤色光源を合わせて用いることが特に好ましい。
本発明において、ミニLEDはチップサイズ100~200μm角程度のLEDを意味し、マイクロLEDはチップサイズ100μm角未満のLEDを意味する。マイクロLEDとしては、例えば、国際公開第2014/204694号等に記載のマイクロLEDが好ましく挙げられる。
さらに、本発明の波長選択吸収フィルタ中に含有する染料を、前述の通り、4種の染料A~Dを組合わせて含有する形態とした場合には、染料の混合に伴う耐光性の低下を上回る、優れたレベルの耐光性を示すことができる。
つまり、通常、上記表面フィルムとして反射防止機能を有する円偏光板が使用されるところ、本発明の波長選択吸収フィルタを採用することにより、自発光表示装置を含む本発明の表示装置は、円偏光板を用いることなく上記優れた効果を発揮することができる。なお、本発明の表示装置(自発光表示装置を含む。)の構成として、本発明の効果を損なわない範囲で、反射防止フィルムを併用することを妨げるものではない。
上記自発光表示装置において、本発明の波長選択吸収フィルタは、外光とは反対側に位置する面において、粘着剤層を介してガラス(基材)と貼り合わされていることが好ましい。
上記自発光表示装置において、本発明の波長選択吸収フィルタは、外光とは反対側に位置する面において、粘着剤層を介してガラス(基材)と貼り合わされていることが好ましい。
剥離性基材としては、特に制限されず、任意の剥離性基材を使用することができ、例えば上述の本発明の波長選択吸収フィルタの製造方法における剥離フィルムが挙げられる。
その他、塗布、乾燥、熟成及び硬化の条件についても、常法に基づき、適宜調整することができる。
なお、以下の実施例において組成を表す「部」及び「%」は、特に断らない限り質量基準である。また、λmaxは、後記波長選択吸収フィルタの吸光度極大値及び20%値波長の測定において、最大吸光度を示す極大吸収波長を意味する。
波長選択吸収フィルタを、下記の手順に沿って作製した。
波長選択吸収フィルタの作製に用いた材料を次に示す。
<マトリックス樹脂>
(樹脂9)
環状ポリオレフィン樹脂であるアペルAPL6011T(商品名、三井化学社製、エチレンとノルボルネンとの共重合ポリマー、Tg 105℃)を、樹脂9として用いた。
(樹脂10)
環状ポリオレフィン樹脂であるアートンRX4500(商品名、JSR社製、ノルボルネン系ポリマー、Tg 132℃)を、樹脂10として用いた。
(剥離性制御樹脂成分2)
タフテックH1043(商品名、旭化成(株)製、水添スチレン系熱可塑性エラストマー(SEBS))
(剥離性制御樹脂成分3)
タフテックM1943(商品名、旭化成(株)製、水添スチレン系熱可塑性エラストマー(SEBS))
<色素>
染料Aとして下記のE-14、E-24及びE-40並びに国際公開第2014/208749号の実施例で使用されている、下記の化合物例5をそれぞれ用いた。また、染料Bとして下記の7-11及び7-23、染料Cとして下記のC-73及びC-80、染料Dとして下記のF-34及びF-35をそれぞれ用いた。
(会合抑制剤)
会合抑制剤として下記化合物をそれぞれ用いた。
セルロースアシレートフィルム(富士フィルム社製、商品名:ZRD40SL)を基材1として用いた。
(基材4)
ポリエチレンテレフタレートフィルム(三菱ケミカル社製、商品名:ダイアホイルT600E50、膜厚50μm)を基材4として用いた。
<基材つき波長選択吸収フィルタの作製A>
(1)波長選択吸収層形成液Aの調製
各成分を下記に示す組成で混合し、波長選択吸収層形成液Aを調製した。
――――――――――――――――――――――――――――――――――
波長選択吸収層形成液Aの組成
――――――――――――――――――――――――――――――――――
樹脂9 87.4 質量部
剥離性制御樹脂成分2 3.4 質量部
レベリング剤:メガファックF-554(DIC社製、フッ素系ポリマー)
0.16質量部
染料E-40 3.80質量部
会合抑制剤301 5.20質量部
シクロヘキサン(溶媒) 655.0 質量部
酢酸エチル(溶媒) 115.0 質量部
――――――――――――――――――――――――――――――――――
上記濾過処理後の波長選択吸収層形成液Aを、基材1上に、乾燥後の膜厚が1.9μmとなるようにバーコーターを用いて塗布し、120℃で乾燥し、基材つき波長選択吸収フィルタNo.101を作製した。
染料の種類及び添加量、並びに、会合抑制剤の種類及び添加量の少なくともいずれかを下記表1に記載の内容に変更した以外は基材つき波長選択吸収フィルタNo.101の作製と同様にして、基材つき波長選択吸収フィルタNo.102~109及びC201~C204を作製した。
(基材2)
セルロースアシレートフィルム(富士フィルム社製、商品名:ZRD40SL)を、2.3mol/Lの水酸化ナトリウム水溶液に、55℃で3分間浸漬した。室温(25℃)の水洗浴槽中で洗浄し、30℃で0.05mol/Lの硫酸を用いて中和した。再度、室温(25℃)の水洗浴槽中で洗浄し、さらに100℃の温風で乾燥した。このようにして、鹸化処理を行ったセルロースアシレートフィルムを基材2として用いた。
各成分を下記に示す組成で混合し、波長選択吸収層形成液Bを調製した。
――――――――――――――――――――――――――――――――――
波長選択吸収層形成液Bの組成
――――――――――――――――――――――――――――――――――
樹脂10 86.1 質量部
剥離性制御樹脂成分3 3.4 質量部
レベリング剤:メガファックF-554(DIC社製、フッ素系ポリマー)
0.16質量部
染料E-24 3.43質量部
染料7-11 0.53質量部
染料C-73 0.17質量部
染料F-34 2.08質量部
会合抑制剤303 4.10質量部
シクロヘキサン(溶媒) 1018.3 質量部
酢酸エチル(溶媒) 548.3 質量部
――――――――――――――――――――――――――――――――――
上記濾過処理後の波長選択吸収層形成液Bを、基材2上に、乾燥後の膜厚が1.2μmとなるようにバーコーターを用いて塗布し、120℃で乾燥し、基材つき波長選択吸収フィルタNo.110を作製した。
基材の種類、染料の種類及び添加量、並びに、会合抑制剤の種類及び添加量の少なくともいずれかを下記表1に記載の内容に変更した以外は基材つき波長選択吸収フィルタNo.110の作製と同様にして、基材つき波長選択吸収フィルタNo.111~115、C205及びC206を作製した。
染料の欄における「-」の表記は、該当する染料を含有していないことを示す。
染料の含有量は、波長選択吸収フィルタ中における染料の質量基準での含有割合を意味し、単位は質量%である。会合抑制剤の含有量は、波長選択吸収フィルタ中における会合抑制剤の質量基準での含有割合を意味し、単位は質量%である。また、λmaxは後記波長選択吸収フィルタの吸光度極大値及び20%値波長の測定において、最大吸光度を示す染料の吸収極大波長を示す。
化合物例5:国際公開第2014/208749号の実施例で使用されている化合物例5
ガスバリア層と波長選択吸収フィルタの積層体(以下、単に積層体と称す。)を下記の手順に沿って作製した。作製に用いた材料を次に示す。
<樹脂>
(樹脂4)
AQ-4104(クラレ(株)製、エクセバール AQ-4104(商品名)、変性ポリビニルアルコール(結晶性樹脂)、けん化度98~99mol%)
基材つき波長選択吸収フィルタNo.101の、波長選択吸収フィルタ側を、コロナ処理装置(商品名:Corona-Plus、VETAPHONE社製)を用い、放電量1000W・min/m2、処理速度3.2m/minの条件でコロナ処理を施し、基材3として用いた。
(1)樹脂溶液の調製
各成分を下記に示す組成で混合し、90℃の恒温槽で1時間撹拌し、樹脂4を溶解させ、ガスバリア層形成液1を調製した。
――――――――――――――――――――――――――――――――――
ガスバリア層形成液1の組成
――――――――――――――――――――――――――――――――――
樹脂4 4.0質量部
純水 96.0質量部
――――――――――――――――――――――――――――――――――
上記濾過処理後のガスバリア層形成液1を、基材3のコロナ処理を施した面側に、乾燥後の膜厚が1.6μmとなるようにバーコーターを用いて塗布し、120℃60秒で乾燥し、積層体No.101を作製した。
この積層体No.101は、基材1、波長選択吸収フィルタNo.101及びガスバリア層がこの順に積層された構成を有する。
基材つき波長選択吸収フィルタの種類を後記表2のように変更した以外は、積層体No.101の作製と同様にして、積層体No.102~115及びC202~C204を作製した。また、基材つき波長選択吸収フィルタの種類を基材つき波長選択吸収フィルタNo.C201に変更した以外は、積層体No.101の作製と同様にして、積層体No.C201を、基材つき波長選択吸収フィルタの種類を基材つき波長選択吸収フィルタNo.C205に変更した以外は、積層体No.101の作製と同様にして、積層体No.C205を、基材つき波長選択吸収フィルタの種類を基材つき波長選択吸収フィルタNo.C206に変更した以外は、積層体No.101の作製と同様にして、積層体No.C206を、それぞれ作製した。
積層体No.101~115が本発明の波長選択吸収フィルタを含む積層体であり、積層体No.C202~C204が比較の積層体であり、積層体No.C201、C205及びC206が参照用の積層体である。
ガスバリア層の結晶化度、酸素透過度及び厚みについては、以下の方法により評価した。
上記で作製した積層体から、ガスバリア層を2~3mg剥離し、日立ハイテクサイエンス社製のDSC7000X(商品名)を用いて、20℃から260℃の範囲にかけて10℃/minで昇温し、融解熱1を測定した。
J. Appl. Pol. Sci., 81, 762(2001)に記載の方法に基づき、ガスバリア層の結晶化度を算出した。具体的には、上記融解熱1とJ. Appl. Pol. Sci., 81, 762(2001)に記載の完全結晶の融解熱2を用い、以下の式により結晶化度を算出した。
[結晶化度(%)]=([融解熱1]/[融解熱2])×100
このようにして測定した上記積層体No.101~112およびC201~C205のガスバリア層の結晶化度は53%であった。
日立ハイテクノロジーズ社製の電界放出型走査電子顕微鏡S-4800(商品名)を用いて積層体の断面写真を撮影し、厚みを読み取った。
このようにして測定した上記積層体No.101~115およびC201~C206のガスバリア層の厚みは1.6μmであった。
上記積層体No.101~115およびC201~C206の作製において、波長選択吸収フィルタにコロナ処理を施さなかった以外は同様にして積層体を作製した。つぎに、積層体のガスバリア層側に、厚み約20μmの粘着剤1(商品名:SK2057、綜研化学社製)を介して、厚み80μmのトリアセチルセルロースフィルム(商品名:フジタックTD80UL、富士フイルム社製)を貼合した。続いて基材3に相当する、基材1、基材2又は基材4と、波長選択吸収フィルタとを剥離することにより、トリアセチルセルロースフィルム、粘着剤1及びガスバリア層がこの順に積層されてなる、酸素透過度評価膜No.L101~L115およびLC201~LC206を調製した。
酸素透過率測定装置としてMOCON社製のOX-TRAN 2/21(商品名)を用いて、等圧法(JIS K 7126-2)により25℃、相対湿度50%、酸素分圧1atm、測定面積50cm2の条件で、酸素透過度評価膜の酸素透過度を測定した。
このようにして測定した上記積層体No.L101~L115およびLC201~LC206の酸素透過度は0.6cc/m2・day・atmであった。
作製した各基材つき波長選択吸収フィルタの吸光度極大値及び20%値波長A又はD並びに各積層体の耐光性について、下記のようにして測定、評価した。結果を表2にまとめて示す。
(波長選択吸収フィルタの吸光度)
島津製作所(株)製のUV360分光光度計(商品名)を用いて、基材つき波長選択吸収フィルタの、380~800nmの波長範囲における吸光度を、1nmごとに測定した。基材つき波長選択吸収フィルタの各波長λnmにおける吸光度Abx(λ)と、染料を含有しない基材つき波長選択吸収フィルタ(すなわち、No.C201、C205あるいはC206の波長選択吸収フィルタ)の吸光度Ab0(λ)との吸光度差、Abx(λ)-Ab0(λ)を算出した。
なお、基材つき波長選択吸収フィルタNo.101~109及びC202~C204においては、染料を含有しない基材つき波長選択吸収フィルタとしてNo.C201の基材つき波長選択吸収フィルタを用い、基材つき波長選択吸収フィルタNo.110~112においては、染料を含有しない基材つき波長選択吸収フィルタとしてNo.C205の基材つき波長選択吸収フィルタを用い、基材つき波長選択吸収フィルタNo.113~115においては、染料を含有しない基材つき波長選択吸収フィルタとしてNo.C206の基材つき波長選択吸収フィルタを用いた。
(λmaxの決定)
上記のAbx(λ)-Ab0(λ)に基づき、極大吸収波長λmaxを決定した。
(20%値波長の決定)
続いて、上記のAbx(λ)-Ab0(λ)において、波長390~440nmに主吸収波長帯域を有する色素を含む場合には、波長390~440nmにおける吸光度極大値に対して20%の吸光度を与える二つの波長のうち長波長側の波長(20%値波長A)を求めた。また、波長680~680nmに主吸収波長帯域を有する色素を含む場合には、波長680~780nmにおける吸光度極大値に対して20%の吸光度を与える二つの波長のうち短波長側の波長(20%値波長D)を求めた。
(耐光性評価膜の作製)
積層体のガスバリア層側に、厚み約20μmの粘着剤1(商品名:SK2057、綜研化学社製)を介して、厚み60μmのトリアセチルセルロースフィルム(商品名:フジタックTG60UL、富士フイルム社製)を貼合した。続いて、基材1、基材2あるいは基材4を剥がし、基材1、基材2あるいは基材4を貼り合わせていた波長選択吸収フィルタ側に、上記粘着剤1を介してガラスを貼合し、耐光性評価膜を作製した。
得られた耐光性評価膜は、ガラス/粘着剤1の層/波長選択吸収フィルタ/ガスバリア層/粘着剤1の層/トリアセチルセルロースフィルムの順に積層された構成を有する。
島津製作所(株)製のUV3600分光光度計(商品名)により、耐光性評価膜の、200~1000nmの波長範囲における吸光度を、1nmごとに測定した。耐光性評価膜の各波長における吸光度と、染料及び会合抑制剤を含有しない点以外は同じ構成である耐光性評価膜の吸光度との吸光度差を算出し、この吸光度差の最大値を吸収極大値として定義した。
なお、積層体No.101~109及びC202~C204の耐光性評価膜においては、染料及び会合抑制剤を含有しない積層体No.C201の耐光性評価膜を用いて吸光度差を算出し、積層体No.110~112の耐光性評価膜においては、染料及び会合抑制剤を含有しない積層体No.C205の耐光性評価膜を用いて吸光度差を算出し、積層体No.113~115の耐光性評価膜においては、染料及び会合抑制剤を含有しない積層体No.C206の耐光性評価膜を用いて吸光度差を算出した。
(耐光性)
耐光性評価膜を(株)スガ試験機社製のスーパーキセノンウェザーメーターSX75(商品名)で、60℃、相対湿度50%の環境下において200時間光を照射し、この照射前後における各吸収極大値を測定し、以下の式により耐光性を算出した。
[耐光性(%)]=([200時間光照射後の吸収極大値]/[光照射前の吸収極大値])×100
20%値波長評価の欄および耐光性評価の欄における「-」の表記は、該当する染料を含有していないことを示す。
波長390~440nmに主吸収波長帯域を有する染料Aを含有する場合、会合抑制剤を含有しない比較の積層体No.C202では、20%値波長Aは456nmと本発明で規定する範囲外であり、キセノン200時間照射後の残存率は73%と低かった。また、本発明で規定する染料Aと会合抑制剤を含有するものの、20%値波長Aは465nmと本発明で規定する範囲外である比較の積層体No.C204は、キセノン200時間照射後の残存率は73%と低かった。
これらに対して、本発明で規定する染料Aと会合抑制剤を含有し、20%値波長Aが455nm以下である積層体No.101~108、110、111及び113~115は、いずれも染料Aのキセノン200時間照射後の残存率は79%以上であり、優れた耐光性を示していた。
また、波長680~780nmに主吸収波長帯域を有する染料Dを含有する場合、会合抑制剤を含有しない比較の積層体No.C203では、20%値波長Dは639nmと本発明で規定する範囲外であり、キセノン200時間照射後の残存率は91%であった。
これに対して、本発明で規定する染料Dと会合抑制剤を含有し、20%値波長Dが640nm以上である積層体No.109~114は、いずれも染料Dのキセノン200時間照射後の残存率は95%であり、耐光性に優れていた。
特に、表1及び2の結果を総合すると、染料Aとして同じ染料E-40を使用するNo.C202とNo.101~108との対比、及び、染料Dとして同じ染料F-34を使用するNo.C203とNo.109~112との対比から、本発明で規定する会合抑制剤の添加によって、吸収極大波長(λmax)に変化が生じることなく吸収波形が先鋭化され、この結果、優れた耐光性が得られていることがわかる。また、カルボン酸アミド化合物を会合抑制剤として使用するNo.105~107の中では、シクロヘキサン環を有する会合抑制剤を使用するNo.107の耐光性は87%、ベンゼン環を有する会合抑制剤を使用するNo.106の耐光性は92%と、環構造を有しない会合抑制剤を使用するNo.105と比較して、より優れた耐光性が得られていることがわかる。
92 ガスバリア層
93 積層体
Claims (10)
- 樹脂と、色素と、カルボン酸エステル結合、カルボン酸アミド結合、スルホン酸アミド結合、ウレタン結合及びスルホニル結合の少なくともいずれか1つの極性基を有し、分子量が1000以下である化合物とを含み、
前記色素が、下記に示す染料A及び染料Dの少なくとも一方を含み、
前記染料Aを含む場合は、波長390~440nmにおける吸光度極大値に対して、20%の吸光度を与える二つの波長のうち長波長側の波長が455nm以下であり、
前記染料Dを含む場合は、波長680~780nmにおける吸光度極大値に対して、20%の吸光度を与える二つの波長のうち短波長側の波長が640nm以上である、
波長選択吸収フィルタ。
染料A:波長390~440nmに主吸収波長帯域を有する色素
染料D:波長680~780nmに主吸収波長帯域を有する色素 - 前記色素が、前記染料Aおよび前記染料Dの両方を含む、請求項1に記載の波長選択吸収フィルタ。
- 前記の極性基を有する化合物が、カルボン酸エステル結合を有する化合物である、請求項1~4のいずれか1項に記載の波長選択吸収フィルタ。
- 前記の極性基を有する化合物が、カルボン酸アミド結合を有する化合物である、請求項1~4のいずれか1項に記載の波長選択吸収フィルタ。
- 前記樹脂がポリスチレン樹脂を含む、請求項1~6のいずれか1項に記載の波長選択吸収フィルタ。
- 前記樹脂が環状ポリオレフィン樹脂を含む、請求項1~6のいずれか1項に記載の波長選択吸収フィルタ。
- 請求項1~8のいずれか1項に記載の波長選択吸収フィルタを含む表示装置。
- 前記表示装置が自発光表示装置である、請求項9に記載の表示装置。
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