WO2021124905A1 - Composite polarization plate and liquid crystal display device - Google Patents
Composite polarization plate and liquid crystal display device Download PDFInfo
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- WO2021124905A1 WO2021124905A1 PCT/JP2020/045007 JP2020045007W WO2021124905A1 WO 2021124905 A1 WO2021124905 A1 WO 2021124905A1 JP 2020045007 W JP2020045007 W JP 2020045007W WO 2021124905 A1 WO2021124905 A1 WO 2021124905A1
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- polarizing plate
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- acrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Definitions
- the present invention relates to a composite polarizing plate and a liquid crystal display device using the same.
- Patent Documents 1 to 5 it is known to improve the brightness of a liquid crystal display device by using a composite polarizing plate in which a polarizing plate and a brightness improving film are laminated. Further, in recent years, with the increase in size of mobile terminals such as smartphones, in order to realize long-term driving with a limited battery capacity, light utilization efficiency has been improved by using a brightness improving film.
- An object of the present invention is to provide a composite polarizing plate capable of suppressing appearance defects even in a high temperature durability test and a liquid crystal display device using the same.
- the present invention provides the following composite polarizing plate and liquid crystal display device.
- a composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
- the first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
- a composite polarizing plate having a tensile elastic modulus of 1.5 GPa or more at a temperature of 23 ° C. and a relative humidity of 55% of the buffer layer.
- the composite polarizing plate according to [1] wherein the buffer layer and the brightness improving film are bonded to each other via a second pressure-sensitive adhesive layer.
- the resin film includes a film made of at least one resin selected from the group consisting of a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. Polarizer.
- the buffer layer is a cured product layer of a resin composition containing a curable component.
- the composite polarizing plate of the present invention is a composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
- the first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
- the tensile elastic modulus at a temperature of the buffer layer of 23 ° C. and a relative humidity of 55% is 1.5 GPa or more.
- the brightness improving film reflects linearly polarized light of a predetermined polarization axis or circularly polarized light in a predetermined direction among the incident natural light and the like, and other light can be transmitted. Therefore, in a composite polarizing plate in which a brightness improving film and a polarizing plate including a linearly polarizing layer are laminated, light from a light source such as a backlight of a liquid crystal display device or the like is incident to obtain transmitted light in a predetermined polarized state. Light other than the predetermined polarized state can be reflected without being transmitted.
- the light reflected on the brightness-improving film surface is further inverted via a reflection layer or the like provided behind the brightness-improving film surface.
- the amount of light transmitted through the luminance improving film can be increased by re-inciding the light on the luminance improving film and transmitting a part or all of the light as light in a predetermined polarized state. Further, by supplying polarized light that is difficult to be absorbed by the linear polarizing layer to the polarizing plate, the amount of light that can be used for image display or the like can be increased, and the brightness in the liquid crystal display device can be improved.
- the composite polarizing plate including the brightness improving film and the polarizing plate as described above the light such as the backlight can be efficiently used for the image display of the liquid crystal display device in the liquid crystal display device or the like, and the screen is brightened. can do.
- the buffer layer contained in the composite polarizing plate may be a resin film or a cured product layer of a resin composition containing a curable component.
- the tensile elastic modulus of the buffer layer may be 3 GPa or more, 5 GPa or more, usually 10 GPa or less, and 8 GPa or less.
- the tensile modulus can be measured by the method described in Examples described later.
- the tensile elastic modulus when the buffer layer is a cured product layer can be measured by the following procedure.
- the resin composition is applied to the release-treated surface of the release-treated polyethylene terephthalate film (hereinafter, may be referred to as “PET film”) using an applicator so that the thickness after drying is 100 ⁇ m.
- PET film polyethylene terephthalate film
- tensile elastic modulus may be measured by the method described in the examples described above.
- the wrinkles generated in the brightness improving film after the high temperature durability test are caused by the shrinkage of the polarizing plate in a high temperature environment.
- a buffer layer is interposed between the polarizing plate and the brightness improving film. Since the buffer layer has a tensile elastic modulus in the above range, it is not easily deformed. Therefore, even if the polarizing plate shrinks when the high-temperature durability test of the composite polarizing plate is performed, the polarizing plate shrinks due to the presence of a buffer layer that is not easily deformed between the polarizing plate and the brightness improving film. Along with this, it is possible to suppress the shrinkage of the brightness improving film.
- the in-plane retardation Re (590) of the buffer layer at a wavelength of 590 nm is preferably 20 nm or less, may be 10 nm or less, may be 5 nm or less, or may be 0 nm.
- Re (590) of the buffer layer is within the above range, it is possible to suppress a decrease in viewing angle characteristics when the composite polarizing plate is applied to a liquid crystal display device.
- the in-plane retardation Re (590) can be measured by the method described in Examples described later.
- the buffer layer is a cured product layer except that the thickness after drying is the actual thickness of the buffer layer contained in the composite polarizing plate.
- a sample for measurement may be prepared according to the procedure for preparing a sample for measurement used for measuring the tensile elastic modulus of the case, and the measurement may be carried out by the method described in Examples described later.
- the first pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer for bonding the protective layer of the polarizing plate and the buffer layer.
- the first pressure-sensitive adhesive layer is provided so as to be in direct contact with both the protective layer and the buffer layer of the polarizing plate.
- FIG. 1 and 2 are schematic cross-sectional views schematically showing an example of the composite polarizing plate of the present embodiment.
- the composite polarizing plate 1 of the present embodiment the polarizing plate 10, the first pressure-sensitive adhesive layer 31, the buffer layer 15a, the second pressure-sensitive adhesive layer 32, and the brightness improving film 18 are laminated in this order.
- the second pressure-sensitive adhesive layer 32 is a pressure-sensitive adhesive layer for adhering the buffer layer 15a and the brightness-improving film 18, so that the second pressure-sensitive adhesive layer 32 is in contact with both the buffer layer 15a and the brightness-improving film 18. It is provided in.
- the polarizing plates 10 shown in FIGS. 1 and 2 are arranged on the opposite side of the first protective layer 12 arranged on the brightness improving film 18 side of the linearly polarizing layer 11 and the brightness improving film 18 side of the linearly polarizing layer 11. It has a second protective layer 13.
- the polarizing plate 10 may have a first protective layer 12 and may not have a second protective layer 13.
- the composite polarizing plate 1 may have a third pressure-sensitive adhesive layer 33 on the side of the polarizing plate 10 opposite to the brightness improving film 18 side.
- the third pressure-sensitive adhesive layer 33 can be used for bonding the composite polarizing plate 1 to the liquid crystal cell in the liquid crystal display device described later.
- the composite polarizing plate 1 may further have a release film 35 for covering and protecting the surface of the third pressure-sensitive adhesive layer 33 on the side of the third pressure-sensitive adhesive layer 33 opposite to the polarizing plate 10 side ( Figure 2).
- the buffer layer 15a provided on the composite polarizing plate 1 is preferably a resin film.
- the resin film is preferably formed of a resin material having excellent transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, etc., and the resin material is preferably a thermoplastic resin. preferable.
- the resin film may have a single-layer structure or a multi-layer structure.
- the resin film may be a stretched film. For example, the tensile elastic modulus can be adjusted by selecting the type of resin constituting the resin film, stretching the resin film, and the like.
- the details of the resin (resin material) for forming the resin film constituting the buffer layer 15a will be described later, but at least one selected from a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. It is preferable to use a film made of the above resin.
- the first protective layer 12 side of the polarizing plate 10 and the buffer layer 15a are bonded together by the first pressure-sensitive adhesive layer 31, and the second pressure-sensitive adhesive layer 15a and the brightness improving film 18 are bonded together. It can be obtained by laminating with the agent layer 32.
- the composite polarizing plate 1 has the third pressure-sensitive adhesive layer 33, for example, a pressure-sensitive adhesive sheet having the third pressure-sensitive adhesive layer 33 formed on the release film 35 may be laminated on the polarizing plate 10.
- FIGS. 3 and 4 are schematic cross-sectional views schematically showing another example of the composite polarizing plate of the present embodiment.
- the polarizing plate 10 the first pressure-sensitive adhesive layer 31, the buffer layer 15b, and the brightness improving film 18 are laminated in this order.
- the polarizing plates 10 shown in FIGS. 3 and 4 are arranged on the opposite side of the first protective layer 12 arranged on the brightness improving film 18 side of the linearly polarizing layer 11 and the brightness improving film 18 side of the linearly polarizing layer 11. It has a second protective layer 13.
- the polarizing plate 10 may have a first protective layer 12 and may not have a second protective layer 13.
- the composite polarizing plate 2 has a third pressure-sensitive adhesive layer 33 and a release film 35 in this order on the side of the polarizing plate 10 opposite to the brightness improving film 18 side, as described in the composite polarizing plate 1 shown in FIG. It may be (Fig. 4).
- the buffer layer 15b provided on the composite polarizing plate 2 is provided so as to be in direct contact with the brightness improving film 18 without interposing another layer such as an adhesive layer.
- the buffer layer 15b is preferably a cured product layer of a resin composition containing a curable component.
- the buffer layer 15b which is a cured product layer, can be formed, for example, by applying the above resin composition to one side of the brightness improving film 18 and curing the curable component.
- the tensile elastic modulus can be adjusted within the above range by selecting, for example, the type of curable component.
- the details of the curable component constituting the buffer layer 15b will be described later, but it is more preferable that the cured product layer is a resin composition containing an active energy ray-curable compound as the curable component.
- the buffer layer 15b side of the laminate in which the buffer layer 15b is formed on the brightness improving film 18 and the first protective layer 12 side of the polarizing plate 10 are bonded by the first adhesive layer 31.
- the composite polarizing plate 2 has the third pressure-sensitive adhesive layer 33, for example, the third pressure-sensitive adhesive layer 33 can be provided by the method described in the case where the composite polarizing plate 1 is provided with the third pressure-sensitive adhesive layer 33.
- the liquid crystal display devices 5 and 6 of the present embodiment include the composite polarizing plate 1 or the composite polarizing plate 2 described above, a liquid crystal cell 41, and usually a backlight 42.
- the composite polarizing plates 1 and 2 are preferably provided on the backlight 42 side (opposite side to the viewing side) of the liquid crystal cell 41.
- the composite polarizing plates 1 and 2 are provided with a third pressure-sensitive adhesive layer 33 on the polarizing plate 10 side so that the brightness improving film 18 side is arranged on the backlight 42 side. It is preferable that the film is laminated on the liquid crystal cell 41 via.
- the composite polarizing plates 1 and 2 include the brightness improving film 18 as described above, the light of the backlight 42 is efficiently displayed on the liquid crystal. It can be used to display images of devices 5 and 6, and can brighten the screen.
- the composite polarizing plates 1 and 2 have the above-mentioned cushioning layers 15a and 15b having a tensile elastic modulus, respectively, appearance defects are unlikely to occur when a high temperature durability test is performed. As a result, the liquid crystal display devices 5 and 6 having the composite polarizing plate 1 or the composite polarizing plate 2 can suppress the deterioration of visibility even when exposed to high temperature conditions.
- the buffer layer has a tensile elastic modulus in the above range.
- the buffer layer preferably has an in-plane retardation Re (590) in the above range.
- the buffer layer may be a resin film or a cured product layer of a resin composition containing a curable component.
- the thickness of the buffer layer is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, further preferably 30 ⁇ m or more, and usually 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less. There may be.
- the resin material (resin) constituting the resin film is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, and the like.
- the resin material is preferably a thermoplastic resin.
- a resin material is not particularly limited, and is, for example, a cellulose ester resin; a (meth) acrylic acid resin; an olefin resin such as a chain aliphatic olefin resin or a cyclic olefin resin; a polyvinyl chloride resin.
- Resin styrene resin; acrylonitrile / butadiene / styrene resin; acrylonitrile / styrene resin; polyvinyl acetate resin; polyvinylidene chloride resin; polyamide resin; polyacetal resin; polycarbonate resin; modified polyphenylene ether resin; Polybutylene teflate-based resin, polyester-based resin such as polyethylene teftalate-based resin; polysulfone-based resin; polyether sulfone-based resin; polyarylate-based resin; polyamideimide-based resin; polyimide-based resin, etc. Species or a combination of two or more species can be used.
- a resin selected from a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin.
- (meth) acrylic means that it may be either acrylic or methacryl.
- (Meta) "(Meta)” such as acryloyl has the same meaning.
- the resin material constituting the resin film can be used after performing any appropriate polymer modification, and the polymer modification includes, for example, copolymerization, cross-linking, molecular terminalization, stereoregularity control, and dissimilar polymers. Modifications such as mixing, including cases involving a reaction, can be mentioned.
- cellulose ester-based resin a part or all of hydrogen atoms in the hydroxyl group of cellulose obtained from raw material cellulose such as cotton linter and wood pulp (perforated tree pulp, coniferous tree pulp) are replaced with acetyl group, propionyl group and / or butyryl group.
- it is a cellulose organic acid ester or a cellulose mixed organic acid ester.
- those composed of acetic acid ester of cellulose, propionic acid ester, butyric acid ester, mixed ester thereof and the like can be mentioned.
- triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
- the (meth) acrylic acid-based resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer.
- Specific examples of the (meth) acrylic resin include poly (meth) acrylic acid esters such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymers; methyl methacrylate- (meth) acrylic acid esters.
- the (meth) acrylic acid-based resin may have a structural unit that expresses positive birefringence. If it has a structural unit that expresses positive birefringence and a structural unit that expresses negative birefringence, the position of the film formed from the (meth) acrylic acid-based resin can be adjusted by adjusting the abundance ratio thereof. The phase difference can be controlled, and a (meth) acrylic acid-based resin film having a low phase difference can be obtained.
- a structural unit constituting a lactone ring, polycarbonate, polyvinyl alcohol, cellulose acetate, polyester, polyarylate, polyimide, polyolefin, etc. is represented by the general formula (1) described later.
- Structural units can be mentioned.
- Examples of the structural unit that expresses negative birefringence include structural units derived from styrene-based monomers, maleimide-based monomers, etc., polymethylmethacrylate structural units, structural units represented by the general formula (3) described later, and the like. Can be mentioned.
- a (meth) acrylic acid-based resin having a lactone ring structure or a glutarimide structure is preferably used.
- a (meth) acrylic acid-based resin having a lactone ring structure or a glutarimide structure has excellent heat resistance. More preferably, it is a (meth) acrylic acid-based resin having a glutarimide structure.
- Examples of the (meth) acrylic acid-based resin having a glutarimide structure include JP-A-2006-309033, JP-A-2006-317560, and JP-A-2006-328329. , JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492, JP-A-2006-337493, JP-A-2006-337569, JP-A-2007-9182, It is described in Kai 2009-161744. These statements are incorporated herein by reference.
- the glutarimide resin is preferably a structural unit represented by the following general formula (1) (hereinafter, also referred to as “glutarimide unit”) and a structural unit represented by the following general formula (2) (hereinafter, “( Meta) Also referred to as "acrylic acid ester unit”).
- R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. It is a substituent containing 3 to 12 cycloalkyl groups or an aromatic ring having 5 to 15 carbon atoms.
- R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 6 is hydrogen, an alkyl group having 1 to 18 carbon atoms, and 3 carbon atoms. It is a substituent containing a cycloalkyl group of up to 12 or an aromatic ring having 5 to 15 carbon atoms.
- the glutarimide resin may further contain a structural unit represented by the following general formula (3) (hereinafter, also referred to as “aromatic vinyl unit”), if necessary.
- R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 8 is an aryl group having 6 to 10 carbon atoms
- R 1 and R 2 are independently hydrogen or methyl groups, and R 3 is hydrogen, methyl group, butyl group, or cyclohexyl group, and more preferably.
- R 1 is a methyl group
- R 2 is a hydrogen
- R 3 is a methyl group.
- the glutarimide resin is a glutarimide unit, may include only a single type, R 1 in the general formula (1), R 2, and R 3 also include a plurality of different types Good.
- the glutarimide unit can be formed by imidizing the (meth) acrylic acid ester unit represented by the above general formula (2).
- the glutarimide unit is an acid anhydride such as maleic anhydride, or a half ester of such an acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms; crotonic acid, methacrylic acid, maleic acid. It can also be formed by imidizing ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, and citraconic acid.
- R 4 and R 5 are independently hydrogen or methyl groups
- R 6 is hydrogen or methyl group
- R 5 is a methyl group
- R 6 is a methyl group.
- Glutarimide resin as (meth) acrylic acid ester unit may include only a single type, include R 4, R 5, and a plurality of types of R 6 are different in the above general formula (2) You may be.
- the glutarimide resin preferably contains styrene, ⁇ -methylstyrene and the like as the aromatic vinyl unit represented by the above general formula (3), and more preferably contains styrene.
- the glutarimide resin may contain only a single type as the aromatic vinyl unit, or may contain a plurality of types in which R 7 and R 8 in the above general formula (3) are different.
- the content of the glutarimide unit in glutarimide resin is preferably, for example, vary depending on the structure and the like of R 3.
- the content of the glutarimide unit is preferably 1% by weight to 80% by weight, more preferably 1% by weight to 70% by weight, still more preferably 1% by weight, based on the total structural unit of the glutarimide resin. It is about 60% by weight, and particularly preferably 1% by weight to 50% by weight.
- a low phase difference (meth) acrylic resin film having excellent heat resistance can be obtained.
- the content of the aromatic vinyl unit in the glutarimide resin can be appropriately set according to the purpose and required properties. Depending on the application, the content of the aromatic vinyl unit may be zero.
- the content thereof is preferably 10% by weight to 80% by weight, more preferably 20% by weight to 80% by weight, based on the glutarimide unit of the glutarimide resin. It is more preferably 20% by weight to 60% by weight, and particularly preferably 20% by weight to 50% by weight.
- a (meth) acrylic acid-based resin film having a low phase difference and excellent heat resistance and mechanical strength can be obtained.
- the glutarimide resin may be further copolymerized with other structural units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit.
- Other structural units include, for example, a structure composed of nitrile-based monomers such as acrylonitrile and methacrylonitrile; maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. The unit is mentioned.
- These other structural units may be directly copolymerized or graft-copolymerized in the glutarimide resin.
- the olefin-based resin is composed of a structural unit derived from a chain aliphatic olefin such as ethylene and propylene, or an alicyclic olefin such as norbornene or a substitute thereof (hereinafter, these are collectively referred to as a norbornene-based monomer). It is a resin.
- the olefin resin may be a copolymer using two or more kinds of monomers.
- a cyclic olefin resin which is a resin mainly containing a constituent unit derived from an alicyclic olefin is preferably used.
- Typical examples of the alicyclic olefin constituting the cyclic olefin resin include norbornene-based monomers.
- Norbornene is a compound in which one carbon-carbon bond of norbornane is a double bond, and is named bicyclo [2,2,1] hept-2-ene according to the IUPAC nomenclature. is there.
- substitution product of norbornene examples include 3-substituted product, 4-substituted product, 4,5-di-substituted product, etc., with the double bond position of norbornene at the 1,2-position, and further.
- Dicyclopentadiene, dimethanooctahydronaphthalene and the like can also be mentioned.
- the cyclic olefin resin may or may not have a norbornane ring as its constituent unit.
- Examples of the norbornene-based monomer forming a cyclic olefin-based resin having no norbornene ring as a constituent unit include those having a 5-membered ring by ring-opening, typically norbornene, dicyclopentadiene, 1- or 4-. Examples thereof include methylnorbornene and 4-phenylnorbornene.
- the cyclic olefin-based resin is a copolymer, the arrangement state of the molecule is not particularly limited, and it may be a random copolymer, a block copolymer, or a graft. It may be a polymer.
- the cyclic olefin resin include, for example, a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer, and addition of maleic acid and cyclopentadiene to them.
- examples thereof include polymer modified products made, and polymers or copolymers obtained by hydrogenating them; addition polymers of norbornene-based monomers, and addition copolymers of norbornene-based monomers and other monomers.
- examples of other monomers used as copolymers include ⁇ -olefins, cycloalkenes, non-conjugated dienes and the like.
- the cyclic olefin resin may be a copolymer using one or more of norbornene-based monomers and other alicyclic olefins.
- a ring-opening polymer using a norbornene-based monomer or a resin obtained by hydrogenating a ring-opening copolymer is preferably used.
- the resin material constituting the above-mentioned resin film may contain an appropriate additive as long as the transparency is not impaired.
- Additives include, for example, antioxidants, UV absorbers, antistatic agents, lubricants, nucleating agents, antifogging agents, antiblocking agents, phase difference reducing agents, stabilizers, processing aids, plasticizers, impact resistant aids. , Matters, antibacterial agents, antifungal agents and the like. A plurality of kinds of these additives may be used in combination.
- any optimum method may be appropriately selected.
- a solvent casting method in which a resin dissolved in a solvent is cast on a metal band or drum and the solvent is dried and removed to obtain a film. The resin is heated above its melting temperature, kneaded and extruded from a die.
- a melt extrusion method for obtaining a film by cooling, and the like in the melt extrusion method, a single-layer film can be extruded, or a multilayer film can be extruded at the same time.
- the resin film may be a stretched film that has been stretched.
- the tensile elastic modulus may be adjusted to a desired range by performing a stretching process. Examples of the stretching treatment include uniaxial stretching and biaxial stretching.
- the curable component contained in the resin composition is an active energy ray-curable compound that is cured by irradiation with active energy rays, or a cured product by heating. It is preferably a thermosetting cured product.
- the curable component is more preferably an active energy ray-curable compound.
- the active energy ray curable compound examples include an electron beam curable compound, an ultraviolet curable compound, and a visible light curable compound. Of these, an ultraviolet curable compound or a visible light curable compound is preferable, and an ultraviolet curable compound is more preferable.
- the resin composition containing the ultraviolet curable compound or the visible light curable compound may be a radical polymerization type resin composition or a cationic polymerization type resin composition.
- ultraviolet rays refer to active energy rays having a wavelength in the range of 10 nm or more and less than 380 nm, and visible light means active energy rays having a wavelength of 380 nm or more and 800 nm or less.
- the radically polymerizable resin composition contains a radically polymerizable compound as a curable component.
- the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
- the radically polymerizable compound either a monofunctional radically polymerizable compound or a bifunctional or higher functional radically polymerizable compound can be used.
- the radically polymerizable compound may be used alone or in combination of two or more.
- a compound having a (meth) acryloyl group is suitable.
- Examples of the monofunctional radically polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group.
- the (meth) acrylamide derivative is preferable in terms of ensuring the adhesiveness between the brightness-improving film and the cured product layer, and also in terms of high polymerization rate and excellent productivity.
- Specific examples of the (meth) acrylamide derivative include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N.
- N-N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N- N-Hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide can be mentioned.
- heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle include N-acrylloylmorpholine, N-acrylloylpiperidin, N-methacryloylpiperidin, and N-acrylloylpyrolidin. Can be mentioned.
- an N-hydroxyalkyl group-containing (meth) acrylamide derivative is preferable from the viewpoint of adhesiveness, and N-hydroxyalkyl group-containing (meth) acrylamide derivative is particularly preferable. Hydroxyethyl (meth) acrylamide is preferred.
- Examples of the monofunctional radically polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group.
- Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (meth).
- Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
- Hydroxyalkyl (meth) acrylates such as meta) acrylates, 6-hydroxyhexyl (meth) acrylates, 8-hydroxyoctyl (meth) acrylates, 10-hydroxydecyl (meth) acrylates, 12-hydroxylauryl (meth) acrylates; [4 -(Hydroxymethyl) cyclohexyl] Methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and other hydroxyl group-containing (meth) acrylate; glycidyl (meth) acrylate, 4-hydroxybutyl (Meta) Acrylate Group-containing (meth) acrylate such as glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl
- Oxetane group-containing (meth) acrylates such as ruoxetanyl methyl (meth) acrylate and 3-hexyl oxetanyl methyl (meth) acrylate; having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate (meth) Acrylate; Neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate; p-phenylphenol (meth) acrylate and the like can be mentioned.
- Examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- Examples of the monofunctional radically polymerizable compound include lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, and vinylpyrrole. , Vinyl imidazole, vinyl oxazole, vinyl morpholin, and other vinyl-based monomers having a nitrogen-containing heterocycle.
- a radically polymerizable compound having an active methylene group can be used as the monofunctional radically polymerizable compound.
- a radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group at the terminal or in the molecule and having an active methylene group.
- the active methylene group include an acetoacetyl group, an alkoxymalonyl group, a cyanoacetyl group and the like, and the active methylene group is preferably an acetoacetyl group.
- radically polymerizable compound having an active methylene group examples include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetacetoxy-1-methylethyl (meth) acrylate and the like.
- Acetoacetoxyalkyl (meth) acrylate 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl)
- Examples thereof include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like.
- the radically polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
- polyfunctional radical polymerizable compound examples include N, N'-methylenebis (meth) acrylamide, which is a polyfunctional (meth) acrylamide derivative, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di (meth).
- Eesterates 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like can be mentioned.
- Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.), Light Acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd.).
- SR-531 manufactured by Sartomer
- CD-536 manufactured by Sartomer
- the like are preferable.
- the radical polymerization type resin composition may contain various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and various (meth) acrylates, if necessary. ) It may contain an acrylate-based monomer or the like.
- the polyfunctional (meth) acrylamide derivative is preferably contained in the radical polymerization type resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is a cured product is excellent.
- the radically polymerizable compound preferably contains a polyfunctional radically polymerizable compound in order to control the water absorption rate of the cured product of the resin composition.
- a polyfunctional radical-polymerizable compound those having a high logPow value, which will be described later, are preferable.
- the resin composition containing the curable compound for forming the buffer layer preferably has a high octanol / water partition coefficient (hereinafter, may be referred to as “logPow value”).
- the logPow value is an index showing the lipophilicity of a substance, and means the logarithmic value of the partition coefficient of octanol / water.
- a high logPow means that it is lipophilic, that is, it has a low water absorption rate.
- the logPow value can be measured (the flask immersion method described in JIS-Z-7260), but it can also be calculated by calculation. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft Co., Ltd. is used.
- the logPow value of the resin composition can be calculated by the following formula.
- Resin composition logPow ⁇ (logPowi ⁇ Wi) logPower: LogPower value of each component contained in the resin composition Wi: (number of moles of i component) / (total number of moles of resin composition)
- the logPow value of the resin composition is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.
- a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound should be used in combination from the viewpoint of achieving both the adhesiveness between the brightness improving film and the cured product layer and the optical durability in a harsh environment. Is preferable. Usually, it is preferable to use the monofunctional radical polymerizable compound in an amount of 3 to 80% by weight and the polyfunctional radical polymerizable compound in an amount of 20 to 97% by weight based on 100% by weight of the radically polymerizable compound.
- the radical polymerization type resin composition contains an active energy ray-curable component as a curable component, it can be used as a composition containing an active energy ray-curable compound.
- the radical polymerization type resin composition preferably contains a photopolymerization initiator.
- a photopolymerization initiator contained in the radical polymerization type resin composition a photopolymerization initiator that is cleaved by ultraviolet rays or visible light can be used.
- a photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy).
- Aromatic ketone compounds such as -2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexylphenylketone; methoxyacetophenone, 2,2- Acetphenone compounds such as dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1, etc .; benzoin methyl ether, benzoin Benzophenone ether compounds such as ethyl ether, benzoin isopropyl ether, benzoin butyl ether and anisoine methyl ether; aromatic ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalene sulfonyl chloride; 1-phenone- Photoactive oxime compounds such as
- the content of the photopolymerization initiator in the radical polymerization type resin composition is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
- the blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
- the radical polymerization type resin composition contains a visible light curable compound
- Examples of the photopolymerization initiator include a compound represented by the following general formula (4) (hereinafter, may be referred to as “compound (4)”).
- R 11 and R 12 are independently -H, -CH 2 CH 3 , -iPr (isopropyl group) or -Cl, and R 11 and R 12 may be the same as each other. It may be very different. ]
- the compound (4) may be used alone or in combination with a photopolymerization initiator having high sensitivity to light of 380 nm or more, which will be described later.
- the adhesiveness between the brightness improving film and the cured product layer can be improved as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. ..
- diethylthioxanthone in which R 11 and R 12 are ⁇ CH 2 CH 3 is particularly preferable.
- the content of the compound (4) in the radical polymerization type resin composition is preferably 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component (radical polymerizable compound). It is more preferably 5 to 4 parts by weight, and even more preferably 0.9 to 3 parts by weight.
- Examples of the photopolymerization initiator having high sensitivity to light of 380 nm or more include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino.
- the radical polymerization type resin composition preferably contains a compound represented by the following general formula (5) (hereinafter, may be referred to as "compound (5)") in addition to the compound (4).
- R 13 , R 14 and R 15 are independently -H, -CH 3 , -CH 2 CH 3 , -iPr or -Cl, and R 13 , R 14 and R 15 are They may be the same or different from each other. ]
- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE907, manufactured by BASF), which is also a commercially available product, can be preferably used. Is.
- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF)
- 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) is also preferable because of its high sensitivity.
- the radical polymerization type resin composition may contain a polymerization initiation aid, if necessary.
- the polymerization initiator include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and the like. , And ethyl 4-dimethylaminobenzoate is particularly preferable.
- the content of the polymerization initiator in the radical polymerization type resin composition is usually 0 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). , Preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight.
- radical polymerizable compound (a1) having an active methylene group and radical polymerization initiator (a2) having a hydrogen abstraction action When a radically polymerizable compound (a1) having an active methylene group is used as the radically polymerizable compound contained in the radically polymerizable resin composition, it should be used in combination with a radical polymerization initiator (a2) having a hydrogen abstraction action. Is preferable. According to such a radical polymerization type resin composition, good adhesiveness can be ensured even when a cured layer is provided so as to be in direct contact with the brightness improving film, particularly in a high humidity environment. The reason for this is not clear, but it is speculated as follows.
- the radically polymerizable compound (a1) having an active methylene group is incorporated into the main chain and / or side chain of the base polymer in the cured product layer while being polymerized together with other radically polymerizable compounds constituting the cured product layer. Form a cured product layer.
- a radical polymerization initiator (a2) having a hydrogen abstraction action is present, hydrogen is drawn from the radical polymerizable compound (a2) having an active methylene group while forming the base polymer constituting the cured product layer. It is extracted and a radical is generated in the methylene group.
- the methylene group in which radicals are generated reacts with the hydroxyl group of the brightness improving film, and a covalent bond is formed between the cured product layer and the brightness improving film.
- the adhesiveness between the brightness improving film and the cured product layer is improved even in a particularly high humidity environment.
- Examples of the radical polymerization initiator (a2) having a hydrogen abstraction action include a thioxanthone-based radical polymerization initiator and a benzophenone-based radical polymerization initiator.
- the radical polymerization initiator (a2) is preferably a thioxanthone-based radical polymerization initiator.
- Examples of the thioxanthone-based radical polymerization initiator include the above-mentioned compound (4).
- Specific examples of compound (4) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and the like.
- diethylthioxanthone in which R 11 and R 12 are ⁇ CH 2 CH 3 is particularly preferable.
- the radical polymerization type resin composition contains a radical polymerization compound (a1) having an active methylene group and a radical polymerization initiator (a2) having a hydrogen abstraction action
- a curable component (radical polymerizable compound) is contained. ) Is 100% by weight, the radical polymerization compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is added to 100 parts by weight of the total amount of the curable component. It is preferably contained in an amount of 0.1 to 10 parts by weight.
- radicals are generated in the methylene group of the radical polymerizable compound (a1) having an active methylene group, and the methylene group and the brightness improving film are formed. It is considered that the hydroxyl group reacts with the hydroxyl group to form a covalent bond. Therefore, in order to generate a radical in the methylene group of the radically polymerizable compound (a1) having an active methylene group and sufficiently form such a covalent bond, the total amount of the curable component (radical polymerizable compound) is set to 100% by weight.
- the radical polymerizable compound (a1) having an active methylene group is preferably contained in an amount of 1 to 50% by weight, more preferably 3 to 30% by weight.
- the amount of the radically polymerizable compound (a1) having an active methylene group should be 1% by weight or more. Is preferable. On the other hand, if it exceeds 50% by weight, curing failure of the cured product layer may occur.
- the radical polymerization initiator (a2) having a hydrogen abstraction action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. It is more preferable to do so. In order to sufficiently proceed with the hydrogen abstraction reaction, it is preferable to use 0.1 part by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not be completely dissolved in the radical polymerization type resin composition.
- the cationically polymerized resin composition contains a cationically polymerizable compound as a curable component.
- the cationically polymerizable compound is classified into a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. .. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be lowered by containing it in the cationically polymerizable resin composition.
- monofunctional cationically polymerizable compounds often have functional groups that express various functions, and by containing them in a cationically polymerizable resin composition, the resin composition and / or a cured product of the resin composition Various functions can be expressed in the layer.
- the polyfunctional cationically polymerizable compound is preferably contained in the resin composition because the cured product layer can be three-dimensionally crosslinked.
- the blending ratio of the monofunctional cationically polymerizable compound and the polyfunctional cationically polymerizable compound in the cationically polymerizable resin composition is 10 parts by weight or more and 1000 parts by weight or more with respect to 100 parts by weight of the monofunctional cationically polymerizable compound. It is preferably contained in the range of parts by weight or less.
- Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group.
- Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound.
- the alicyclic epoxy is excellent in curability and adhesiveness. It is particularly preferable to contain a compound.
- Examples of the alicyclic epoxy compound include caprolactone-modified products and trimethylcaprolactone-modified products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
- Valerolactone modified products, etc. and specifically, seroxide 2021, seroxide 2021A, seroxide 2021P, seroxide 2081, seroxide 2083, seroxide 2085 (all manufactured by Daicel Chemical Industry Co., Ltd., Cyclocure UVR-6105, CyclohexylUVR). -6107, Cyracure 30, R-6110 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like can be mentioned.
- a compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the cationically polymerized resin composition and lowering the liquid viscosity of the composition.
- Compounds having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, and the like.
- a compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationically polymerized resin composition and lowering the liquid viscosity of the composition.
- examples of compounds having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, and tricyclodecane vinyl ether. , Cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol type tetravinyl ether and the like.
- the cationically polymerizable resin composition contains at least one compound selected from the above-mentioned curable component having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group. Since all of these compounds are cured by cationic polymerization, it is preferable that the cationically polymerizable resin composition further contains a photocationic polymerization initiator.
- This photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group.
- a photoacid generator described later is preferably used as the photocationic polymerization initiator.
- the resin composition containing the curable compound contains a visible light curable compound
- a photocationic polymerization initiator having high sensitivity to light of 380 nm or more, but the photocationic polymerization initiator is generally used. Since it is a compound that exhibits maximum absorption in the wavelength range around 300 nm or shorter, it is possible to add a light sensitizer that exhibits maximum absorption to light in a longer wavelength range, specifically, a wavelength longer than 380 nm. Sensitive to light of a wavelength near this range, it is possible to promote the generation of cation species or acids from the photocationic polymerization initiator.
- the photosensitizer examples include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducing dyes and the like. Two or more types may be mixed and used.
- the anthracene compound is preferable because it has an excellent photosensitizing effect, and specific examples thereof include anthracene UVS-1331 and anthracene UVS-1221 (manufactured by Kawasaki Kasei Chemicals, Inc.).
- the content of the photosensitizer is preferably 0.1% by weight to 5% by weight, more preferably 0.5% by weight to 3% by weight.
- the resin composition containing the active energy ray-curable compound is a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group.
- Additives other than these may be contained.
- these components will be described.
- the radically polymerizable resin composition or the cationically polymerizable resin composition comprises a (meth) acrylic oligomer obtained by polymerizing a (meth) acrylic monomer in addition to a radically polymerizable compound or a cationically polymerizable compound (curable component). Can be contained.
- a (meth) acrylic oligomer in the resin composition the curing shrinkage when the resin composition is irradiated with active energy rays to be cured is reduced, and the cured product layer and the brightness improving film are formed.
- the interfacial stress can be reduced.
- the (meth) acrylic oligomer in order to sufficiently suppress the curing shrinkage of the cured product layer, it is preferable to contain 3 parts by weight or more of the (meth) acrylic oligomer with respect to 100 parts by weight of the total amount of the curable component, and 5 parts by weight or more is contained. Is preferable. If the content of the (meth) acrylic oligomer in the resin composition is too large, the reaction rate when the resin composition is irradiated with active energy rays is drastically reduced, which may result in poor curing.
- the (meth) acrylic oligomer In order to sufficiently suppress a decrease in the reaction rate, it is preferable to contain 20 parts by weight or less of the (meth) acrylic oligomer, and 15 parts by weight or less, based on 100 parts by weight of the total amount of the curable component. Is more preferable.
- the (meth) acrylic oligomer also has a low viscosity. Is preferable.
- the (meth) acrylic oligomer having a low viscosity and capable of preventing the curing shrinkage of the cured product layer those having a weight average molecular weight (Mw) of 15,000 or less are preferable, those having a weight average molecular weight (Mw) of 15,000 or less are more preferable, and those having a weight average molecular weight (Mw) of 10,000 or less are more preferable. Those are particularly preferable.
- the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and 1500 or more. Is particularly preferable.
- Examples of the (meth) acrylic monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2-methyl-2.
- the (meth) acrylic oligomer examples include “ARUFON” manufactured by Toagosei Co., Ltd., “Actflow” manufactured by Soken Chemical Co., Ltd., and “JONCRYL” manufactured by BASF Japan Ltd.
- the logPow value of the (meth) acrylic oligomer is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
- the resin composition containing the active energy ray-curable compound can contain a photoacid generator.
- the photoacid generator can be represented by the following general formula (6).
- L + represents any onium cation.
- X - is, PF 6 -, SbF 6 - , AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, dithiocarbamate anion, SCN - counter anion more selected from the group consisting of Represents.
- PF 6 ⁇ , SbF 6 ⁇ , or AsF 6 ⁇ is preferable, and PF 6 ⁇ or SbF 6 ⁇ is more preferable.
- Preferred onium salts constituting the photoacid generator include, for example, "Cyracure UVI-6992", “Cyracure UVI-6974” (all manufactured by Dow Chemical Japan Co., Ltd.), “Adeka Putmer SP150”, and “” ADEKA OPTMER SP152 ”,“ ADEKA OPTMER SP170 ”,“ ADEKA PTMER SP172 ”(above, manufactured by ADEKA Corporation),“ IRGACURE250 ”(manufactured by Ciba Specialty Chemicals),“ CI-5102 ”,“ CI-2855 (Above, manufactured by Nippon Soda Co., Ltd.), "Sun Aid SI-60L", “Sun Aid SI-80L”, “Sun Aid SI-100L”, “Sun Aid SI-110L”, “Sun Aid SI-180L” (above, Sanshin Kagaku) (Made by), “CPI-100P”, “CPI-100A” (above, manufactured by Sun Appro Co., Ltd.
- the photoacid generator is 10 parts by weight or less, and 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.
- the resin composition containing an active energy ray-curable compound can contain a compound containing an epoxy group or an alkoxy group together with a photoacid generator.
- Examples of the compound containing an epoxy group include a compound having one or more epoxy groups in the molecule or a compound having two or more epoxy groups in the molecule, even if it is a polymer compound (epoxy resin). Good. When these compounds are used, a compound having two or more functional groups having reactivity with an epoxy group in the molecule may be used in combination. Examples of the functional group having reactivity with the epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
- Examples of the compound having one or more epoxy groups in the molecule include an epoxy resin, a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, and a bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin.
- Bisphenol S type epoxy resin Bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene
- Polyfunctional epoxy resin such as type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin; glycidyl ester type epoxy resin; glycidylamine type epoxy resin; hidden toin type epoxy resin; There are isocyanurate type epoxy resins; aliphatic chain epoxy resins and the like, and these epoxy resins may be halogenated or hydrogenated.
- the epoxy resin products on the market are not particularly limited, but for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, DIC manufactured by Japan Epoxy Resin Co., Ltd. Epicron 830, EXA835LV, HP4032D, HP820 manufactured by ADEKA Co., Ltd., EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Serokiside series manufactured by Daicel Chemical Co., Ltd.
- Epoxide series EHPE series, YD series, YDF series, YDCN series, YDB series manufactured by Nippon Steel Chemical Co., Ltd., phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, which has epoxy groups at both ends; YP series, etc.), Denacol series manufactured by Nagase ChemteX Corporation, Epoxy series manufactured by Kyoeisha Chemical Co., Ltd., etc. Two or more of these epoxy resins may be used in combination.
- the compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. Examples of such compounds include melamine compounds, amino resins, silane coupling agents and the like.
- the compound containing an epoxy group or an alkoxy group is usually contained in an amount of 30 parts by weight or less and 20 parts by weight or less based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. Is preferable. If the content of the compound containing an epoxy group or an alkoxy group is too large, the adhesiveness of the cured product layer to the luminance improving film may be lowered, and the impact resistance to the drop test may be deteriorated. From the viewpoint of water resistance, the compound containing an epoxy group or an alkoxy group preferably contains 2 parts by weight or more, and 5 parts by weight or more, based on 100 parts by weight of the total amount of the curable component contained in the resin composition. Is more preferable.
- the resin composition containing the active energy ray-curable compound can contain a silane coupling agent.
- the silane coupling agent is preferably an active energy ray-curable compound, but even if it is not an active energy ray-curable compound, water resistance can be imparted to the cured product layer.
- Examples of the active energy ray-curable silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltri.
- silane coupling agent having an amino group As the silane coupling agent that is not active energy ray curable, a silane coupling agent having an amino group is preferable.
- the silane coupling agent having an amino group include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyl.
- non-active energy ray-curable silane coupling agent examples include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis. (Triethoxysilylpropyl) Tetrasulfide, 3-isocyanatepropyltriethoxysilane, imidazolesilane and the like can be mentioned.
- silane coupling agent having an amino group only one type may be used, or two or more types may be used in combination.
- the silane coupling agent preferably contains 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is more preferable to contain parts, and it is further preferable to contain 0.1 to 10 parts by weight. If the content of the silane coupling agent is too large, the storage stability of the resin composition deteriorates, and if the content of the silane coupling agent is too small, the effect of adhesive water resistance is not easily exhibited.
- the resin composition containing the active energy ray-curable compound can contain a compound having a vinyl ether group.
- a compound having a vinyl ether group By containing a compound having a vinyl ether group, the adhesive water resistance between the brightness improving film and the cured product layer can be improved. It is presumed that this is because the vinyl ether group interacts with the brightness improving film to increase the adhesive force.
- a radically polymerizable compound As the compound having a vinyl ether group.
- the compound having a vinyl ether group is preferably contained in an amount of 0.1 to 19 parts by weight based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound.
- the resin composition containing the active energy ray-curable compound includes a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group, in addition to the above-mentioned compounds having a vinyl ether group.
- Various additives may be contained as long as the object and effect of the present invention are not impaired.
- additives examples include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based oligomers.
- Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surface activity Agents; plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like.
- the logPow value of the above-mentioned additive is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
- the additive usually contains 0 to 10 parts by weight and preferably 0 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is more preferable to include ⁇ 3 parts by weight.
- thermosetting compound a thermosetting adhesive, a hot melt adhesive, or the like can be used from the viewpoint of adhesiveness between the brightness improving film and the cured product layer.
- specific examples include natural rubber adhesives, ⁇ -olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resin adhesives.
- Vinyl chloride resin solvent adhesive chloroprene rubber adhesive, cyanoacrylate adhesive, silicone adhesive, styrene-butadiene rubber solvent adhesive, nitrile rubber adhesive, nitrocellulose adhesive, reactive hot Melt adhesive, phenol resin adhesive, modified silicone adhesive, polyester hot melt adhesive, polyamide resin hot melt adhesive, polyimide adhesive, polyurethane resin hot melt adhesive, polyolefin resin hot melt adhesive, poly Vinyl acetate resin solvent-based adhesive, polystyrene resin solvent-based adhesive, polyvinyl alcohol-based adhesive, polyvinylpyrrolidone resin-based adhesive, polyvinyl butyral-based adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent-based adhesive, melamine resin Examples thereof include based adhesives, urea resin based adhesives, resorcinol based adhesives and the like. Such an adhesive can be used alone or in combination of two or more, and a base polymer corresponding to the type of the adhesive is used.
- thermosetting adhesive develops adhesive strength by being thermoset and solidified by heating.
- examples of the thermosetting adhesive include epoxy-based thermosetting adhesives, urethane-based thermosetting adhesives, acrylic-based thermosetting adhesives, and the like.
- the curing temperature of the thermosetting adhesive is, for example, 100 to 200 ° C.
- the hot melt adhesive is melted or softened by heating, heat-sealed to the brightness improving film, and then solidified by cooling to adhere to the brightness improving film.
- the hot melt adhesive include rubber hot melt adhesives, polyester hot melt adhesives, polyolefin hot melt adhesives, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, and polyurethane resins.
- Examples include hot melt adhesives.
- the softening temperature (ring ball method) of the hot melt adhesive is, for example, 100 to 200 ° C.
- the melt viscosity of the hot melt adhesive is 180 ° C., for example, 100 to 30,000 mPa ⁇ s.
- the linearly polarized light layer has a property of transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis when unpolarized light is incident.
- the linearly polarizing layer preferably contains a polyvinyl alcohol (hereinafter, may be abbreviated as “PVA”)-based resin film.
- PVA polyvinyl alcohol
- linearly polarizing layer containing the PVA-based resin film examples include a polyvinyl alcohol (hereinafter, may be abbreviated as "PVA") -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film.
- PVA polyvinyl alcohol
- examples thereof include those obtained by subjecting a hydrophilic polymer film such as, etc. to a dyeing treatment with a bicolor substance such as iodine or a bicolor dye, and a stretching treatment. Since it is excellent in optical characteristics, it is preferable to use a linearly polarizing layer obtained by dyeing a PVA-based resin film with iodine and uniaxially stretching it.
- the polyvinyl alcohol-based resin can be produced by saponifying the polyvinyl acetate-based resin.
- the polyvinyl acetate-based resin can be a copolymer of polyvinyl acetate, which is a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and another monomer copolymerizable with vinyl acetate.
- Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
- the saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
- the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
- the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.
- a film formed of such a polyvinyl alcohol-based resin is used as a raw film for a linearly polarizing layer.
- the method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
- the film thickness of the polyvinyl alcohol-based resin raw film is, for example, about 10 to 100 ⁇ m, preferably about 10 to 60 ⁇ m, and more preferably about 15 to 30 ⁇ m.
- a linear polarizing layer containing a PVA-based resin film As another method for producing a linear polarizing layer containing a PVA-based resin film, first prepare a base film, apply a resin solution such as a polyvinyl alcohol-based resin on the base film, and dry the base film to remove the solvent. Examples thereof include a step of forming a resin layer on the base film.
- a primer layer can be formed in advance on the surface of the base film on which the resin layer is formed.
- a resin film such as PET can be used as the base film.
- the material of the primer layer include a resin obtained by cross-linking a hydrophilic resin used for the linearly polarizing layer.
- the amount of solvent such as water content of the resin layer is adjusted, then the base film and the resin layer are uniaxially stretched, and then the resin layer is dyed with a bicolor dye such as iodine to obtain two colors.
- the sex dye is adsorbed and oriented on the resin layer.
- the resin layer in which the dichroic dye is adsorbed and oriented is treated with a boric acid aqueous solution, and a washing step of washing off the boric acid aqueous solution is performed.
- a film of a resin layer in which the dichroic dye is adsorption-oriented, that is, a linearly polarizing layer is produced.
- a known method can be adopted for each step.
- the uniaxial stretching of the base film and the resin layer may be performed before dyeing, during dyeing, or during boric acid treatment after dyeing, and each of these multiple steps is uniaxial. Stretching may be performed.
- the base film and the resin layer may be uniaxially stretched in the MD direction (film transport direction), in this case, uniaxially stretched between rolls having different peripheral speeds, or uniaxially stretched using a thermal roll. You may. Further, the base film and the resin layer may be uniaxially stretched in the TD direction (direction perpendicular to the film transport direction), and in this case, the so-called tenter method can be used.
- the stretching of the base film and the resin layer may be a dry stretching in which the resin layer is stretched in the air, or a wet stretching in which the resin layer is swollen with a solvent.
- the draw ratio is 4 times or more, preferably 5 times or more, and particularly preferably 5.5 times or more. There is no particular upper limit to the draw ratio, but it is preferably 8 times or less from the viewpoint of suppressing breakage and the like.
- the linearly polarized light layer produced by the above method can be obtained by laminating a protective layer described later and then peeling off the base film.
- the thickness of the linearly polarizing layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more.
- the thickness of the linearly polarizing layer is 50 ⁇ m or less, preferably 40 ⁇ m or less, and may be 30 ⁇ m or less.
- the linearly polarizing layer has a first protective layer or a first protective layer and a second protective layer (hereinafter, first protective layer and second protective layer) via a known pressure-sensitive adhesive layer or adhesive layer on one or both sides thereof. Can be collectively referred to as a "protective layer") to form a polarizing plate.
- This polarizing plate is a so-called linear polarizing plate.
- the protective layer that can be laminated on one side or both sides of the linearly polarizing layer is formed of, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, stretchability, and the like. Film is used.
- thermoplastic resins include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether sulfone resins; polysulfone resins; polycarbonate resins; polyamides such as nylon and aromatic polyamides.
- the resin compositions of the two protective layers may be the same or different.
- the film formed from the thermoplastic resin may be surface-treated (for example, corona-treated) in order to improve the adhesion to the linearly polarizing layer, and the primer layer (also referred to as the undercoat layer) is thin. Layers may be formed.
- the protective layer may be, for example, one in which the above-mentioned thermoplastic resin is stretched or one in which the above-mentioned thermoplastic resin is not stretched (hereinafter, may be referred to as “unstretched resin”).
- Examples of the stretching treatment include uniaxial stretching and biaxial stretching.
- Examples of the pressure-sensitive adhesive layer used for laminating the protective layer on the linearly polarized light layer include the pressure-sensitive adhesive described in the first pressure-sensitive adhesive layer and the like described later.
- a known adhesive can be used as the adhesive layer used for laminating the protective layer on the linearly polarized light layer.
- Examples of the adhesive include adhesives other than pressure-sensitive adhesives (adhesives), such as water-based adhesives and active energy ray-curable adhesives.
- Examples of the water-based adhesive include an adhesive in which a polyvinyl alcohol-based resin is dissolved or dispersed in water.
- active energy ray-curable adhesive examples include solvent-free active energy ray-curable adhesives containing a curable compound that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. Can be mentioned.
- Brightness improvement film a polarization conversion element having a function of separating the emitted light from a light source such as a backlight into transmitted polarized light and reflected polarized light or scattered polarized light is used.
- the brightness improving film can improve the emission efficiency of linearly polarized light by utilizing the retrolight from the light source of reflected polarized light or scattered polarized light.
- An anisotropic reflection polarizer can be used as the brightness improving film.
- Anisotropy reflectors transmit linearly polarized light of a predetermined polarization axis and reflect other light, such as a multilayer film of dielectrics and a multilayer laminate of layers having different refractive anisotropies. It reflects either left-handed or right-handed circularly polarized light and transmits other light, such as those exhibiting properties, an oriented film of cholesteric liquid crystal polymer or one in which the oriented liquid crystal layer is supported on a film substrate. Those showing characteristics and the like can be mentioned.
- the types of layers constituting the anisotropic reflection polarizer may be two or more.
- Examples of the brightness improving film include a material that generates a phase difference due to stretching represented by polyethylene naphthalate, polyethylene terephthalate, and polycarbonate, an acrylic resin represented by polymethylmethacrylate, and "Arton” manufactured by JSR Corporation.
- a laminate obtained by uniaxially stretching a resin obtained by alternately laminating a resin having a small amount of phase difference expression such as a norbornene-based resin typified by (registered trademark) can be used.
- Specific examples of such a structure include "DBEF” (registered trademark), "APF-V4" (product name), "APF-V3" (product name) and “APF-V2" (product name) manufactured by 3M. First name) and so on.
- the brightness improving film may be, for example, a laminate of a cholesteric liquid crystal layer and a ⁇ / 4 plate.
- Specific examples of such a laminate include the trade name "PCF" manufactured by Nitto Denko KK.
- the brightness improving film may be a reflective grid polarizer.
- the reflection grid polarizer include a metal grid reflection polarizer in which the metal is finely processed to generate reflected polarized light even in the visible light region.
- the thickness of the luminance improving film is usually 5 ⁇ m or more and may be 10 ⁇ m or more, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, and may be 35 ⁇ m or less.
- the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer are layers composed of a pressure-sensitive adhesive.
- the "adhesive” exhibits adhesiveness by sticking itself to an adherend such as a polarizing plate or a liquid crystal layer, and is a so-called pressure-sensitive adhesive. ..
- the active energy ray-curable pressure-sensitive adhesive described later can adjust the degree of cross-linking and the adhesive force by irradiating with energy rays.
- a conventionally known pressure-sensitive adhesive having excellent optical transparency can be used without particular limitation.
- a pressure-sensitive adhesive having a base polymer such as an acrylic type, a urethane type, a silicone type, or a polyvinyl ether type is used. be able to. Further, it may be an active energy ray-curable pressure-sensitive adhesive, a thermosetting pressure-sensitive adhesive or the like.
- an adhesive based on an acrylic resin having excellent transparency, adhesive strength, removability (hereinafter, also referred to as reworkability), weather resistance, heat resistance and the like is preferable.
- the pressure-sensitive adhesive layer is preferably composed of a reaction product of a pressure-sensitive adhesive composition containing a (meth) acrylic resin, a cross-linking agent, and a silane compound, and may contain other components.
- the pressure-sensitive adhesive layer may be formed by using an active energy ray-curable pressure-sensitive adhesive.
- the active energy ray-curable pressure-sensitive adhesive is a harder pressure-sensitive adhesive by blending a pressure-sensitive adhesive composition with an ultraviolet-curable compound such as a polyfunctional acrylate, forming a pressure-sensitive adhesive layer, and then irradiating the pressure-sensitive adhesive with ultraviolet rays to cure the pressure-sensitive adhesive. Layers can be formed.
- the active energy ray-curable pressure-sensitive adhesive has a property of being cured by being irradiated with energy rays such as ultraviolet rays and electron beams.
- the activated energy ray-curable adhesive Since the activated energy ray-curable adhesive has adhesiveness even before irradiation with energy rays, it adheres to an adherend such as an optical film or a liquid crystal layer, and is cured by irradiation with energy rays to improve adhesion.
- a pressure-sensitive adhesive having adjustable properties.
- the active energy ray-curable pressure-sensitive adhesive generally contains an acrylic pressure-sensitive adhesive and an energy ray-polymerizable compound as main components.
- a cross-linking agent is further blended, and if necessary, a photopolymerization initiator, a photosensitizer, or the like can be blended.
- the storage elastic modulus of the pressure-sensitive adhesive layer is preferably 0.10 to 10.0 MPa, more preferably 0.15 to 5.0 MPa at 23 ° C.
- the storage elastic modulus at 23 ° C. is 0.10 MPa or more, problems such as peeling can be suppressed when a temperature change occurs, which is preferable. Further, when it is 10.0 MPa or less, the durability is less likely to be lowered due to the decrease in the adhesive strength, which is preferable.
- the storage elastic modulus of the pressure-sensitive adhesive layer can be measured by the method described in Examples.
- the thickness of the pressure-sensitive adhesive layer is preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more.
- the thickness of the pressure-sensitive adhesive layer is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the release film covers and protects the pressure-sensitive adhesive layer or supports the pressure-sensitive adhesive layer, and has a function as a separator that can be peeled off from the pressure-sensitive adhesive layer.
- Examples of the release film include a film in which the surface of the base film on the pressure-sensitive adhesive layer side is subjected to a mold release treatment such as a silicone treatment.
- Examples of the resin material forming the base film include the same resin materials as those forming the protective layer described above.
- the resin film may have a one-layer structure or may be a multilayer resin film having a multilayer structure of two or more layers.
- In-plane retardation Re (590) at a wavelength of 590 nm of the buffer layer was measured using AxoScan (manufactured by Axometrics, Inc.).
- the measurement sample was pulled in the MD length direction at a tensile speed of 1 mm / min, and from the slope of the initial straight line in the obtained stress-strain curve, the temperature was 23 ° C. and the relative humidity was 55%.
- the tensile elasticity [GPa] in the MD length direction was calculated.
- Example 1 (Preparation of linearly polarized light layer) A 75 ⁇ m-thick polyvinyl alcohol film made of polyvinyl alcohol having an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched about 5 times by a dry method, and 60 while maintaining a tense state. After immersing in pure water at ° C. for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds.
- Adhesive preparation 50 g of a modified PVA resin containing an acetoacetyl group (manufactured by Mitsubishi Chemical Corporation: Gosenex Z-410) was dissolved in 950 g of pure water, heated at 90 ° C. for 2 hours and then cooled to room temperature to obtain a PVA solution. .. Next, a PVA solution, maleic acid, glyoxal, and pure water were blended so that each compound had the following concentration to prepare a PVA-based adhesive. PVA 3.0% by weight Maleic acid 0.01% by weight Glyoxal 0.15% by weight
- a first protective layer a triacetyl cellulose film having a thickness of 40 ⁇ m [trade name “KC4UYW” manufactured by Konica Minolta Opto Co., Ltd.]
- a second protective layer acrylic resin film with a thickness of 40 ⁇ m [trade name “HX-40NE” manufactured by Toyo Steel Co., Ltd.]
- a commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 ⁇ m is bonded to the first protective layer side of the polarizing plate obtained above to form the first pressure-sensitive adhesive layer.
- a triacetyl cellulose film [trade name "TJ40UL” manufactured by Fujifilm Co., Ltd.] as a buffer layer was attached to the opposite side.
- a commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 ⁇ m is bonded to the side of the buffer layer opposite to the first pressure-sensitive adhesive layer side to form a second pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer is buffered.
- a brightness improving film (“AFP-V3 HCS” manufactured by 3M Co., Ltd.) was attached to the side opposite to the layer side. Further, on the second protective layer side of the polarizing plate, a pressure-sensitive adhesive layer (referred to as a third pressure-sensitive adhesive layer) of an acrylic pressure-sensitive adhesive having a thickness of 25 ⁇ m is formed on a release film (thickness 38 ⁇ m, polyethylene terephthalate film). The adhesive layer side of the agent sheet was bonded.
- a pressure-sensitive adhesive layer referred to as a third pressure-sensitive adhesive layer of an acrylic pressure-sensitive adhesive having a thickness of 25 ⁇ m is formed on a release film (thickness 38 ⁇ m, polyethylene terephthalate film).
- a corona treatment was performed on the bonded surface of each material.
- the in-plane retardation Re (590) of the triacetyl cellulose film used as the buffer layer at a wavelength of 590 nm was measured and found to be 0.5 nm.
- the tensile elastic modulus of the buffer layer at a temperature of 23 ° C. and a relative humidity of 55% was 5200 MPa. Further, when the obtained composite polarizing plate was subjected to a high temperature durability test, no wrinkles were observed on the brightness improving film, and the appearance of the composite polarizing plate was good.
- Example 1 A release film, a third pressure-sensitive adhesive layer, and a polarizing plate (from the third pressure-sensitive adhesive layer side, a second protective layer, linearly polarized light) in the same manner as in Example 1 except that a buffer layer and a second pressure-sensitive adhesive layer are not provided.
- a composite polarizing plate in which a layer, a first protective layer were laminated in this order), a first pressure-sensitive adhesive layer, and a brightness improving film were laminated in this order was obtained.
- the obtained composite polarizing plate was subjected to a high temperature durability test, many fine wrinkles were confirmed at the end on the long side of the brightness improving film.
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Abstract
The objective of the present invention is to provide a composite polarization plate with which external appearance defects can be suppressed even in a high-temperature durability test, and a liquid crystal display device using the same. This composite polarization plate comprises a brightness improvement film and a polarization plate having a protective layer on at least one of the surfaces of a linear polarization layer. Layered on the protective layer side of the polarization plate are a first adhesive layer, a buffer layer, and the brightness improvement film, in this order. The tensile modulus of elasticity of the buffer layer, at a temperature of 23°C and a relative humidity of 55%, is 1.5 GPa or higher.
Description
本発明は、複合偏光板及びこれを用いた液晶表示装置に関する。
The present invention relates to a composite polarizing plate and a liquid crystal display device using the same.
従来、偏光板と輝度向上フィルムとを積層した複合偏光板を用いて、液晶表示装置の輝度を向上させることが知られている(特許文献1~5)。また、近年、スマートフォン等のモバイル端末の大型化に伴い、限られたバッテリー容量で長時間の駆動を実現するために、輝度向上フィルムを用いて光の利用効率を上げることが行われている。
Conventionally, it is known to improve the brightness of a liquid crystal display device by using a composite polarizing plate in which a polarizing plate and a brightness improving film are laminated (Patent Documents 1 to 5). Further, in recent years, with the increase in size of mobile terminals such as smartphones, in order to realize long-term driving with a limited battery capacity, light utilization efficiency has been improved by using a brightness improving film.
上記のような複合偏光板は、高温耐久試験を行うと輝度向上フィルムにシワが発生し、複合偏光板に外観不良が発生することが見出された。このような外観不良は、複合偏光板を液晶表示装置に適用した場合に、視認性が低下する原因となり得る。
It was found that when the above-mentioned composite polarizing plate was subjected to a high temperature durability test, wrinkles were generated in the brightness improving film and the composite polarizing plate had a poor appearance. Such poor appearance can cause a decrease in visibility when the composite polarizing plate is applied to a liquid crystal display device.
本発明は、高温耐久試験においても外観不良を抑制することができる複合偏光板及びこれを用いた液晶表示装置の提供を目的とする。
An object of the present invention is to provide a composite polarizing plate capable of suppressing appearance defects even in a high temperature durability test and a liquid crystal display device using the same.
本発明は、以下の複合偏光板及び液晶表示装置を提供する。
〔1〕 直線偏光層の少なくとも片面に保護層を有する偏光板と、輝度向上フィルムと、を有する複合偏光板であって、
前記偏光板の前記保護層側に、第1粘着剤層、緩衝層、及び前記輝度向上フィルムがこの順に積層されており、
前記緩衝層の温度23℃、相対湿度55%における引張弾性率は、1.5GPa以上である、複合偏光板。
〔2〕 前記緩衝層と前記輝度向上フィルムとは、第2粘着剤層を介して貼合されている、〔1〕に記載の複合偏光板。
〔3〕 前記緩衝層は、樹脂フィルムである、〔1〕又は〔2〕に記載の複合偏光板。
〔4〕 前記樹脂フィルムは、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂からなる群より選ばれる少なくとも1種の樹脂からなるフィルムを含む、〔3〕に記載の複合偏光板。
〔5〕 前記緩衝層は、前記輝度向上フィルムに直接接している、〔1〕に記載の複合偏光板。
〔6〕 前記緩衝層は、硬化性成分を含む樹脂組成物の硬化物層である、〔1〕又は〔5〕に記載の複合偏光板。
〔7〕 前記硬化性成分は、活性エネルギー線硬化性化合物を含む、〔6〕に記載の複合偏光板。
〔8〕 前記緩衝層の波長590nmにおける面内レタデーションRe(590)は、20nm以下である、〔1〕~〔7〕のいずれかに記載の複合偏光板。
〔9〕 前記第1粘着剤層は、前記偏光板の前記保護層と前記緩衝層とを貼合している、〔1〕~〔8〕のいずれかに記載の複合偏光板。
〔10〕 前記偏光板は、前記直線偏光層の両面に前記保護層を有する、〔1〕~〔9〕のいずれかに記載の複合偏光板。
〔11〕 前記偏光板の前記輝度向上フィルム側とは反対側に、第3粘着剤層を有する、〔1〕~〔10〕のいずれかに記載の複合偏光板。
〔12〕 前記第3粘着剤層の前記偏光板側とは反対側に剥離フィルムを有する、〔11〕に記載の複合偏光板。
〔13〕 〔1〕~〔12〕のいずれかに記載の複合偏光板と、液晶セルと、を有する液晶表示装置。
〔14〕 さらに、バックライトを有し、
前記複合偏光板は、前記液晶セルと前記バックライトとの間に、前記輝度向上フィルム側が前記バックライト側となるように配置されている、〔13〕に記載の液晶表示装置。 The present invention provides the following composite polarizing plate and liquid crystal display device.
[1] A composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
The first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
A composite polarizing plate having a tensile elastic modulus of 1.5 GPa or more at a temperature of 23 ° C. and a relative humidity of 55% of the buffer layer.
[2] The composite polarizing plate according to [1], wherein the buffer layer and the brightness improving film are bonded to each other via a second pressure-sensitive adhesive layer.
[3] The composite polarizing plate according to [1] or [2], wherein the buffer layer is a resin film.
[4] The composite according to [3], wherein the resin film includes a film made of at least one resin selected from the group consisting of a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. Polarizer.
[5] The composite polarizing plate according to [1], wherein the buffer layer is in direct contact with the brightness improving film.
[6] The composite polarizing plate according to [1] or [5], wherein the buffer layer is a cured product layer of a resin composition containing a curable component.
[7] The composite polarizing plate according to [6], wherein the curable component contains an active energy ray-curable compound.
[8] The composite polarizing plate according to any one of [1] to [7], wherein the in-plane retardation Re (590) of the buffer layer at a wavelength of 590 nm is 20 nm or less.
[9] The composite polarizing plate according to any one of [1] to [8], wherein the first pressure-sensitive adhesive layer is a bonding layer of the protective layer of the polarizing plate and the buffer layer.
[10] The composite polarizing plate according to any one of [1] to [9], wherein the polarizing plate has the protective layers on both sides of the linearly polarizing layer.
[11] The composite polarizing plate according to any one of [1] to [10], which has a third pressure-sensitive adhesive layer on the side of the polarizing plate opposite to the brightness improving film side.
[12] The composite polarizing plate according to [11], which has a release film on the side of the third pressure-sensitive adhesive layer opposite to the polarizing plate side.
[13] A liquid crystal display device including the composite polarizing plate according to any one of [1] to [12] and a liquid crystal cell.
[14] Further, it has a backlight and has a backlight.
The liquid crystal display device according to [13], wherein the composite polarizing plate is arranged between the liquid crystal cell and the backlight so that the brightness improving film side is the backlight side.
〔1〕 直線偏光層の少なくとも片面に保護層を有する偏光板と、輝度向上フィルムと、を有する複合偏光板であって、
前記偏光板の前記保護層側に、第1粘着剤層、緩衝層、及び前記輝度向上フィルムがこの順に積層されており、
前記緩衝層の温度23℃、相対湿度55%における引張弾性率は、1.5GPa以上である、複合偏光板。
〔2〕 前記緩衝層と前記輝度向上フィルムとは、第2粘着剤層を介して貼合されている、〔1〕に記載の複合偏光板。
〔3〕 前記緩衝層は、樹脂フィルムである、〔1〕又は〔2〕に記載の複合偏光板。
〔4〕 前記樹脂フィルムは、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂からなる群より選ばれる少なくとも1種の樹脂からなるフィルムを含む、〔3〕に記載の複合偏光板。
〔5〕 前記緩衝層は、前記輝度向上フィルムに直接接している、〔1〕に記載の複合偏光板。
〔6〕 前記緩衝層は、硬化性成分を含む樹脂組成物の硬化物層である、〔1〕又は〔5〕に記載の複合偏光板。
〔7〕 前記硬化性成分は、活性エネルギー線硬化性化合物を含む、〔6〕に記載の複合偏光板。
〔8〕 前記緩衝層の波長590nmにおける面内レタデーションRe(590)は、20nm以下である、〔1〕~〔7〕のいずれかに記載の複合偏光板。
〔9〕 前記第1粘着剤層は、前記偏光板の前記保護層と前記緩衝層とを貼合している、〔1〕~〔8〕のいずれかに記載の複合偏光板。
〔10〕 前記偏光板は、前記直線偏光層の両面に前記保護層を有する、〔1〕~〔9〕のいずれかに記載の複合偏光板。
〔11〕 前記偏光板の前記輝度向上フィルム側とは反対側に、第3粘着剤層を有する、〔1〕~〔10〕のいずれかに記載の複合偏光板。
〔12〕 前記第3粘着剤層の前記偏光板側とは反対側に剥離フィルムを有する、〔11〕に記載の複合偏光板。
〔13〕 〔1〕~〔12〕のいずれかに記載の複合偏光板と、液晶セルと、を有する液晶表示装置。
〔14〕 さらに、バックライトを有し、
前記複合偏光板は、前記液晶セルと前記バックライトとの間に、前記輝度向上フィルム側が前記バックライト側となるように配置されている、〔13〕に記載の液晶表示装置。 The present invention provides the following composite polarizing plate and liquid crystal display device.
[1] A composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
The first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
A composite polarizing plate having a tensile elastic modulus of 1.5 GPa or more at a temperature of 23 ° C. and a relative humidity of 55% of the buffer layer.
[2] The composite polarizing plate according to [1], wherein the buffer layer and the brightness improving film are bonded to each other via a second pressure-sensitive adhesive layer.
[3] The composite polarizing plate according to [1] or [2], wherein the buffer layer is a resin film.
[4] The composite according to [3], wherein the resin film includes a film made of at least one resin selected from the group consisting of a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. Polarizer.
[5] The composite polarizing plate according to [1], wherein the buffer layer is in direct contact with the brightness improving film.
[6] The composite polarizing plate according to [1] or [5], wherein the buffer layer is a cured product layer of a resin composition containing a curable component.
[7] The composite polarizing plate according to [6], wherein the curable component contains an active energy ray-curable compound.
[8] The composite polarizing plate according to any one of [1] to [7], wherein the in-plane retardation Re (590) of the buffer layer at a wavelength of 590 nm is 20 nm or less.
[9] The composite polarizing plate according to any one of [1] to [8], wherein the first pressure-sensitive adhesive layer is a bonding layer of the protective layer of the polarizing plate and the buffer layer.
[10] The composite polarizing plate according to any one of [1] to [9], wherein the polarizing plate has the protective layers on both sides of the linearly polarizing layer.
[11] The composite polarizing plate according to any one of [1] to [10], which has a third pressure-sensitive adhesive layer on the side of the polarizing plate opposite to the brightness improving film side.
[12] The composite polarizing plate according to [11], which has a release film on the side of the third pressure-sensitive adhesive layer opposite to the polarizing plate side.
[13] A liquid crystal display device including the composite polarizing plate according to any one of [1] to [12] and a liquid crystal cell.
[14] Further, it has a backlight and has a backlight.
The liquid crystal display device according to [13], wherein the composite polarizing plate is arranged between the liquid crystal cell and the backlight so that the brightness improving film side is the backlight side.
本発明によれば、高温耐久試験において外観不良が抑制された複合偏光板及びこれを用いた表示装置を提供することができる。
According to the present invention, it is possible to provide a composite polarizing plate in which an appearance defect is suppressed in a high temperature durability test and a display device using the same.
以下、図面を参照して本発明の複合偏光板及びこれを用いた液晶表示装置の好ましい実施形態について説明する。
Hereinafter, preferred embodiments of the composite polarizing plate of the present invention and a liquid crystal display device using the composite polarizing plate will be described with reference to the drawings.
<複合偏光板>
本発明の複合偏光板は、直線偏光層の少なくとも片面に保護層を有する偏光板と、輝度向上フィルムと、を有する複合偏光板であって、
偏光板の保護層側に、第1粘着剤層、緩衝層、及び輝度向上フィルムがこの順に積層されており、
緩衝層の温度23℃、相対湿度55%における引張弾性率は、1.5GPa以上である。 <Composite polarizing plate>
The composite polarizing plate of the present invention is a composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
The first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
The tensile elastic modulus at a temperature of the buffer layer of 23 ° C. and a relative humidity of 55% is 1.5 GPa or more.
本発明の複合偏光板は、直線偏光層の少なくとも片面に保護層を有する偏光板と、輝度向上フィルムと、を有する複合偏光板であって、
偏光板の保護層側に、第1粘着剤層、緩衝層、及び輝度向上フィルムがこの順に積層されており、
緩衝層の温度23℃、相対湿度55%における引張弾性率は、1.5GPa以上である。 <Composite polarizing plate>
The composite polarizing plate of the present invention is a composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
The first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
The tensile elastic modulus at a temperature of the buffer layer of 23 ° C. and a relative humidity of 55% is 1.5 GPa or more.
輝度向上フィルムは、入射した自然光等の光のうち、所定の偏光軸の直線偏光又は所定の方向の円偏光を反射し、他の光は透過することができる。そのため、輝度向上フィルムと直線偏光層を含む偏光板とを積層した複合偏光板では、液晶表示装置等のバックライト等の光源からの光を入射させて所定の偏光状態の透過光を得るとともに、該所定の偏光状態以外の光は透過せずに反射させることができる。輝度向上フィルム及び直線偏光層を有する複合偏光板を液晶表示装置に用いた場合には、輝度向上フィルム面で反射した光を、更にその後ろ側に設けられた反射層等を介して反転させて輝度向上フィルムに再入射させ、その一部又は全部を所定の偏光状態の光として透過させることにより、輝度向上フィルムを透過する光量の増加を図ることができる。また、直線偏光層に吸収されにくい偏光を偏光板に供給することにより、画像表示等に利用できる光量を増加させることができ、液晶表示装置における輝度を向上させることができる。
The brightness improving film reflects linearly polarized light of a predetermined polarization axis or circularly polarized light in a predetermined direction among the incident natural light and the like, and other light can be transmitted. Therefore, in a composite polarizing plate in which a brightness improving film and a polarizing plate including a linearly polarizing layer are laminated, light from a light source such as a backlight of a liquid crystal display device or the like is incident to obtain transmitted light in a predetermined polarized state. Light other than the predetermined polarized state can be reflected without being transmitted. When a brightness-improving film and a composite polarizing plate having a linearly polarizing layer are used in a liquid crystal display device, the light reflected on the brightness-improving film surface is further inverted via a reflection layer or the like provided behind the brightness-improving film surface. The amount of light transmitted through the luminance improving film can be increased by re-inciding the light on the luminance improving film and transmitting a part or all of the light as light in a predetermined polarized state. Further, by supplying polarized light that is difficult to be absorbed by the linear polarizing layer to the polarizing plate, the amount of light that can be used for image display or the like can be increased, and the brightness in the liquid crystal display device can be improved.
このように、輝度向上フィルムは、直線偏光層に吸収されるような偏光方向を有する光を直線偏光層に入射させずに輝度向上フィルムで一旦反射させ、更にその後ろ側に設けられた反射層等を介して反転させて輝度向上フィルムに再入射させることを繰り返している。これにより、直線偏光層と輝度向上フィルムとの間で反射及び反転した光のうち、直線偏光層を通過し得るような偏光方向になった偏光のみが輝度向上フィルムを透過し、この透過光が直線偏光層に供給され得る。そのため、上記のように輝度向上フィルムと偏光板とを含む複合偏光板を用いることにより、液晶表示装置等においてバックライト等の光を効率的に液晶表示装置の画像表示に使用でき、画面を明るくすることができる。
As described above, in the luminance improving film, light having a polarization direction that is absorbed by the linearly polarizing layer is temporarily reflected by the luminance improving film without being incident on the linearly polarizing layer, and further, a reflecting layer provided behind the linear polarizing layer. It is repeated to invert it and re-enter it on the brightness improving film. As a result, of the light reflected and inverted between the linear polarizing layer and the brightness improving film, only polarized light having a polarization direction capable of passing through the linear polarizing layer passes through the brightness improving film, and this transmitted light is transmitted. It can be supplied to the linearly polarized light layer. Therefore, by using the composite polarizing plate including the brightness improving film and the polarizing plate as described above, the light such as the backlight can be efficiently used for the image display of the liquid crystal display device in the liquid crystal display device or the like, and the screen is brightened. can do.
複合偏光板に含まれる緩衝層は、後述するように、樹脂フィルムであってもよく、硬化性成分を含む樹脂組成物の硬化物層であってもよい。緩衝層の上記引張弾性率は、3GPa以上であってもよく、5GPa以上であってもよく、通常10GPa以下であり、8GPa以下であってもよい。引張弾性率は、後述する実施例に記載の方法によって測定することができる。緩衝層が硬化物層である場合の引張弾性率は、次の手順によって測定することができる。離型処理されたポリエチレンテレフタレートフィルム(以下、「PETフィルム」ということがある。)の離型処理面に、乾燥後の厚みが100μmとなるようにアプリケータを用いて樹脂組成物を塗布する。その後、室温雰囲気下に30分間載置して予備乾燥し、さらに温度100℃の条件下に5分間載置して本乾燥することにより、PETフィルムに塗布された樹脂組成物に含まれる溶剤を十分に揮発させる。最後に、所定の硬化処理(加熱処理や紫外線照射処理等)を行い、PETフィルム上に硬化物層を作製し、PETフィルムを剥離して得られた硬化物層を測定用のサンプルとして、後述する実施例に記載の方法によって引張弾性率を測定すればよい。
As will be described later, the buffer layer contained in the composite polarizing plate may be a resin film or a cured product layer of a resin composition containing a curable component. The tensile elastic modulus of the buffer layer may be 3 GPa or more, 5 GPa or more, usually 10 GPa or less, and 8 GPa or less. The tensile modulus can be measured by the method described in Examples described later. The tensile elastic modulus when the buffer layer is a cured product layer can be measured by the following procedure. The resin composition is applied to the release-treated surface of the release-treated polyethylene terephthalate film (hereinafter, may be referred to as “PET film”) using an applicator so that the thickness after drying is 100 μm. Then, it was placed in a room temperature atmosphere for 30 minutes for pre-drying, and then placed for 5 minutes under the condition of a temperature of 100 ° C. for main drying to remove the solvent contained in the resin composition applied to the PET film. Volatilize well. Finally, a predetermined curing treatment (heat treatment, ultraviolet irradiation treatment, etc.) is performed to prepare a cured product layer on the PET film, and the cured product layer obtained by peeling the PET film is used as a sample for measurement, which will be described later. The tensile elastic modulus may be measured by the method described in the examples described above.
高温耐久試験後の輝度向上フィルムに生じるシワは、高温環境において偏光板が収縮することにより生じることが明らかになった。本実施形態の複合偏光板は、偏光板と輝度向上フィルムとの間に緩衝層が介在している。緩衝層は、上記範囲の引張弾性率を有するため、変形しにくい。そのため、複合偏光板の高温耐久試験を行った場合に偏光板が収縮しても、偏光板と輝度向上フィルムとの間に変形しにくい緩衝層が存在していることにより、偏光板の収縮に伴って輝度向上フィルムが収縮することを抑制することができる。これにより、輝度向上フィルムの端部にシワが発生することを抑制することができるため、高温耐久試験を行った複合偏光板に外観不良が発生することを抑制することができる。また、この複合偏光板を液晶表示装置に適用した場合には、液晶表示装置の画面に表示される画像の視認性が低下することを抑制することができる。
It was clarified that the wrinkles generated in the brightness improving film after the high temperature durability test are caused by the shrinkage of the polarizing plate in a high temperature environment. In the composite polarizing plate of the present embodiment, a buffer layer is interposed between the polarizing plate and the brightness improving film. Since the buffer layer has a tensile elastic modulus in the above range, it is not easily deformed. Therefore, even if the polarizing plate shrinks when the high-temperature durability test of the composite polarizing plate is performed, the polarizing plate shrinks due to the presence of a buffer layer that is not easily deformed between the polarizing plate and the brightness improving film. Along with this, it is possible to suppress the shrinkage of the brightness improving film. As a result, it is possible to suppress the occurrence of wrinkles at the edges of the brightness improving film, and thus it is possible to suppress the occurrence of poor appearance of the composite polarizing plate subjected to the high temperature durability test. Further, when this composite polarizing plate is applied to a liquid crystal display device, it is possible to suppress a decrease in visibility of an image displayed on the screen of the liquid crystal display device.
緩衝層の波長590nmにおける面内レタデーションRe(590)は、20nm以下であることが好ましく、10nm以下であってもよく、5nm以下であってもよく、0nmであってもよい。緩衝層のRe(590)が上記の範囲内であることにより、複合偏光板を液晶表示装置に適用した場合の視野角特性の低下を抑制することができる。面内レタデーションRe(590)は、後述する実施例に記載の方法によって測定することができる。緩衝層が硬化物層である場合の面内レタデーションRe(590)は、乾燥後の厚みを複合偏光板に含まれる緩衝層の実際の厚みとすること以外は、緩衝層が硬化物層である場合の引張弾性率を測定するために用いた測定用のサンプルの作製の手順に沿って、測定用のサンプルを作製し、後述する実施例に記載の方法によって測定すればよい。
The in-plane retardation Re (590) of the buffer layer at a wavelength of 590 nm is preferably 20 nm or less, may be 10 nm or less, may be 5 nm or less, or may be 0 nm. When Re (590) of the buffer layer is within the above range, it is possible to suppress a decrease in viewing angle characteristics when the composite polarizing plate is applied to a liquid crystal display device. The in-plane retardation Re (590) can be measured by the method described in Examples described later. In the in-plane retardation Re (590) when the buffer layer is a cured product layer, the buffer layer is a cured product layer except that the thickness after drying is the actual thickness of the buffer layer contained in the composite polarizing plate. A sample for measurement may be prepared according to the procedure for preparing a sample for measurement used for measuring the tensile elastic modulus of the case, and the measurement may be carried out by the method described in Examples described later.
第1粘着剤層は、偏光板の保護層と緩衝層とを貼合するための粘着剤層であることが好ましい。この場合、第1粘着剤層は、偏光板の保護層及び緩衝層の両方に直接接するように設けられている。
The first pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer for bonding the protective layer of the polarizing plate and the buffer layer. In this case, the first pressure-sensitive adhesive layer is provided so as to be in direct contact with both the protective layer and the buffer layer of the polarizing plate.
以下、上記した複合偏光板の実施形態について具体的に説明する。
〔実施形態1〕
図1及び図2は、本実施形態の複合偏光板の一例を模式的に示す概略断面図である。本実施形態の複合偏光板1は、偏光板10、第1粘着剤層31、緩衝層15a、第2粘着剤層32、及び輝度向上フィルム18がこの順に積層されている。第2粘着剤層32は、緩衝層15aと輝度向上フィルム18とを貼合するための粘着剤層であり、第2粘着剤層32は、緩衝層15a及び輝度向上フィルム18の両方に接するように設けられている。 Hereinafter, embodiments of the above-mentioned composite polarizing plate will be specifically described.
[Embodiment 1]
1 and 2 are schematic cross-sectional views schematically showing an example of the composite polarizing plate of the present embodiment. In the compositepolarizing plate 1 of the present embodiment, the polarizing plate 10, the first pressure-sensitive adhesive layer 31, the buffer layer 15a, the second pressure-sensitive adhesive layer 32, and the brightness improving film 18 are laminated in this order. The second pressure-sensitive adhesive layer 32 is a pressure-sensitive adhesive layer for adhering the buffer layer 15a and the brightness-improving film 18, so that the second pressure-sensitive adhesive layer 32 is in contact with both the buffer layer 15a and the brightness-improving film 18. It is provided in.
〔実施形態1〕
図1及び図2は、本実施形態の複合偏光板の一例を模式的に示す概略断面図である。本実施形態の複合偏光板1は、偏光板10、第1粘着剤層31、緩衝層15a、第2粘着剤層32、及び輝度向上フィルム18がこの順に積層されている。第2粘着剤層32は、緩衝層15aと輝度向上フィルム18とを貼合するための粘着剤層であり、第2粘着剤層32は、緩衝層15a及び輝度向上フィルム18の両方に接するように設けられている。 Hereinafter, embodiments of the above-mentioned composite polarizing plate will be specifically described.
[Embodiment 1]
1 and 2 are schematic cross-sectional views schematically showing an example of the composite polarizing plate of the present embodiment. In the composite
図1及び図2に示す偏光板10は、直線偏光層11の輝度向上フィルム18側に配置される第1保護層12と、直線偏光層11の輝度向上フィルム18側とは反対側に配置される第2保護層13とを有している。偏光板10は、第1保護層12を有し、第2保護層13を有さないものであってもよい。
The polarizing plates 10 shown in FIGS. 1 and 2 are arranged on the opposite side of the first protective layer 12 arranged on the brightness improving film 18 side of the linearly polarizing layer 11 and the brightness improving film 18 side of the linearly polarizing layer 11. It has a second protective layer 13. The polarizing plate 10 may have a first protective layer 12 and may not have a second protective layer 13.
複合偏光板1は、図2に示すように、偏光板10の輝度向上フィルム18側とは反対側に、第3粘着剤層33を有していてもよい。第3粘着剤層33は、後述する液晶表示装置において、複合偏光板1を液晶セルに貼合するために用いることができる。複合偏光板1は、さらに、第3粘着剤層33の偏光板10側とは反対側に、第3粘着剤層33の表面を被覆保護するための剥離フィルム35を有していてもよい(図2)。
As shown in FIG. 2, the composite polarizing plate 1 may have a third pressure-sensitive adhesive layer 33 on the side of the polarizing plate 10 opposite to the brightness improving film 18 side. The third pressure-sensitive adhesive layer 33 can be used for bonding the composite polarizing plate 1 to the liquid crystal cell in the liquid crystal display device described later. The composite polarizing plate 1 may further have a release film 35 for covering and protecting the surface of the third pressure-sensitive adhesive layer 33 on the side of the third pressure-sensitive adhesive layer 33 opposite to the polarizing plate 10 side ( Figure 2).
複合偏光板1に設けられる緩衝層15aは、樹脂フィルムであることが好ましい。樹脂フィルムは、透明性、機械的強度、熱安定性、水分遮蔽性、及び位相差値の安定性等に優れる樹脂材料によって形成されていることが好ましく、樹脂材料は熱可塑性樹脂であることが好ましい。樹脂フィルムは単層構造であってもよく、多層構造であってもよい。樹脂フィルムは、延伸フィルムであってもよい。例えば、樹脂フィルムを構成する樹脂の種類を選択すること、樹脂フィルムに延伸加工を行うこと等により、引張弾性率を調整することができる。緩衝層15aを構成する樹脂フィルムを形成するための樹脂(樹脂材料)の詳細については後述するが、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂から選ばれる少なくとも1種の樹脂からなるフィルムを用いることが好ましい。
The buffer layer 15a provided on the composite polarizing plate 1 is preferably a resin film. The resin film is preferably formed of a resin material having excellent transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, etc., and the resin material is preferably a thermoplastic resin. preferable. The resin film may have a single-layer structure or a multi-layer structure. The resin film may be a stretched film. For example, the tensile elastic modulus can be adjusted by selecting the type of resin constituting the resin film, stretching the resin film, and the like. The details of the resin (resin material) for forming the resin film constituting the buffer layer 15a will be described later, but at least one selected from a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. It is preferable to use a film made of the above resin.
複合偏光板1は、偏光板10の第1保護層12側と緩衝層15aとの間を第1粘着剤層31によって貼合し、緩衝層15aと輝度向上フィルム18との間を第2粘着剤層32によって貼合することによって得ることができる。複合偏光板1が第3粘着剤層33を有する場合は、例えば、剥離フィルム35上に第3粘着剤層33を形成した粘着剤シートを、偏光板10に積層すればよい。
In the composite polarizing plate 1, the first protective layer 12 side of the polarizing plate 10 and the buffer layer 15a are bonded together by the first pressure-sensitive adhesive layer 31, and the second pressure-sensitive adhesive layer 15a and the brightness improving film 18 are bonded together. It can be obtained by laminating with the agent layer 32. When the composite polarizing plate 1 has the third pressure-sensitive adhesive layer 33, for example, a pressure-sensitive adhesive sheet having the third pressure-sensitive adhesive layer 33 formed on the release film 35 may be laminated on the polarizing plate 10.
〔実施形態2〕
図3及び図4は、本実施形態の複合偏光板の他の一例を模式的に示す概略断面図である。本実施形態の複合偏光板2は、偏光板10、第1粘着剤層31、緩衝層15b、及び輝度向上フィルム18がこの順に積層されている。図3及び図4に示す偏光板10は、直線偏光層11の輝度向上フィルム18側に配置される第1保護層12と、直線偏光層11の輝度向上フィルム18側とは反対側に配置される第2保護層13とを有している。偏光板10は、第1保護層12を有し、第2保護層13を有さないものであってもよい。 [Embodiment 2]
3 and 4 are schematic cross-sectional views schematically showing another example of the composite polarizing plate of the present embodiment. In the compositepolarizing plate 2 of the present embodiment, the polarizing plate 10, the first pressure-sensitive adhesive layer 31, the buffer layer 15b, and the brightness improving film 18 are laminated in this order. The polarizing plates 10 shown in FIGS. 3 and 4 are arranged on the opposite side of the first protective layer 12 arranged on the brightness improving film 18 side of the linearly polarizing layer 11 and the brightness improving film 18 side of the linearly polarizing layer 11. It has a second protective layer 13. The polarizing plate 10 may have a first protective layer 12 and may not have a second protective layer 13.
図3及び図4は、本実施形態の複合偏光板の他の一例を模式的に示す概略断面図である。本実施形態の複合偏光板2は、偏光板10、第1粘着剤層31、緩衝層15b、及び輝度向上フィルム18がこの順に積層されている。図3及び図4に示す偏光板10は、直線偏光層11の輝度向上フィルム18側に配置される第1保護層12と、直線偏光層11の輝度向上フィルム18側とは反対側に配置される第2保護層13とを有している。偏光板10は、第1保護層12を有し、第2保護層13を有さないものであってもよい。 [Embodiment 2]
3 and 4 are schematic cross-sectional views schematically showing another example of the composite polarizing plate of the present embodiment. In the composite
複合偏光板2は、偏光板10の輝度向上フィルム18側とは反対側に、図2に示す複合偏光板1において説明したように、第3粘着剤層33及び剥離フィルム35をこの順に有していてもよい(図4)。
The composite polarizing plate 2 has a third pressure-sensitive adhesive layer 33 and a release film 35 in this order on the side of the polarizing plate 10 opposite to the brightness improving film 18 side, as described in the composite polarizing plate 1 shown in FIG. It may be (Fig. 4).
複合偏光板2に設けられる緩衝層15bは、粘着剤層等の他の層を介することなく、輝度向上フィルム18に直接接するように設けられている。緩衝層15bは、硬化性成分を含む樹脂組成物の硬化物層であることが好ましい。硬化物層である緩衝層15bは、例えば、輝度向上フィルム18の片面に、上記樹脂組成物を塗布し硬化性成分を硬化させることによって形成することができる。硬化物層である緩衝層15bは、例えば、硬化性成分の種類を選択することにより、引張弾性率を上記した範囲に調整することができる。緩衝層15bを構成する硬化性成分の詳細については後述するが、硬化性成分として活性エネルギー線硬化性化合物を含む樹脂組成物の硬化物層であることがより好ましい。
The buffer layer 15b provided on the composite polarizing plate 2 is provided so as to be in direct contact with the brightness improving film 18 without interposing another layer such as an adhesive layer. The buffer layer 15b is preferably a cured product layer of a resin composition containing a curable component. The buffer layer 15b, which is a cured product layer, can be formed, for example, by applying the above resin composition to one side of the brightness improving film 18 and curing the curable component. For the buffer layer 15b, which is a cured product layer, the tensile elastic modulus can be adjusted within the above range by selecting, for example, the type of curable component. The details of the curable component constituting the buffer layer 15b will be described later, but it is more preferable that the cured product layer is a resin composition containing an active energy ray-curable compound as the curable component.
複合偏光板2は、輝度向上フィルム18上に緩衝層15bを形成した積層体の緩衝層15b側と、偏光板10の第1保護層12側とを、第1粘着剤層31によって貼合することによって得ることができる。複合偏光板2が第3粘着剤層33を有する場合は、例えば、複合偏光板1に第3粘着剤層33を設ける場合で説明した方法によって第3粘着剤層33を設けることができる。
In the composite polarizing plate 2, the buffer layer 15b side of the laminate in which the buffer layer 15b is formed on the brightness improving film 18 and the first protective layer 12 side of the polarizing plate 10 are bonded by the first adhesive layer 31. Can be obtained by When the composite polarizing plate 2 has the third pressure-sensitive adhesive layer 33, for example, the third pressure-sensitive adhesive layer 33 can be provided by the method described in the case where the composite polarizing plate 1 is provided with the third pressure-sensitive adhesive layer 33.
<液晶表示装置>
図5及び図6は、本実施形態の液晶表示装置の一例を模式的に示す概略断面図である。本実施形態の液晶表示装置5,6は、上記した複合偏光板1又は複合偏光板2と、液晶セル41とを有し、通常バックライト42も有する。複合偏光板1,2は、液晶セル41のバックライト42側(視認側とは反対側)に設けられることが好ましい。この場合、複合偏光板1,2は、図5及び図6に示すように、輝度向上フィルム18側がバックライト42側に配置されように、偏光板10側に設けられた第3粘着剤層33を介して液晶セル41に積層されることが好ましい。 <Liquid crystal display device>
5 and 6 are schematic cross-sectional views schematically showing an example of the liquid crystal display device of the present embodiment. The liquid crystal display devices 5 and 6 of the present embodiment include the compositepolarizing plate 1 or the composite polarizing plate 2 described above, a liquid crystal cell 41, and usually a backlight 42. The composite polarizing plates 1 and 2 are preferably provided on the backlight 42 side (opposite side to the viewing side) of the liquid crystal cell 41. In this case, as shown in FIGS. 5 and 6, the composite polarizing plates 1 and 2 are provided with a third pressure-sensitive adhesive layer 33 on the polarizing plate 10 side so that the brightness improving film 18 side is arranged on the backlight 42 side. It is preferable that the film is laminated on the liquid crystal cell 41 via.
図5及び図6は、本実施形態の液晶表示装置の一例を模式的に示す概略断面図である。本実施形態の液晶表示装置5,6は、上記した複合偏光板1又は複合偏光板2と、液晶セル41とを有し、通常バックライト42も有する。複合偏光板1,2は、液晶セル41のバックライト42側(視認側とは反対側)に設けられることが好ましい。この場合、複合偏光板1,2は、図5及び図6に示すように、輝度向上フィルム18側がバックライト42側に配置されように、偏光板10側に設けられた第3粘着剤層33を介して液晶セル41に積層されることが好ましい。 <Liquid crystal display device>
5 and 6 are schematic cross-sectional views schematically showing an example of the liquid crystal display device of the present embodiment. The liquid crystal display devices 5 and 6 of the present embodiment include the composite
複合偏光板1又は複合偏光板2を有する液晶表示装置5,6では、上記したように、複合偏光板1,2が輝度向上フィルム18を含むため、バックライト42の光を効率的に液晶表示装置5,6の画像表示に使用でき、画面を明るくすることができる。
In the liquid crystal display devices 5 and 6 having the composite polarizing plate 1 or the composite polarizing plate 2, since the composite polarizing plates 1 and 2 include the brightness improving film 18 as described above, the light of the backlight 42 is efficiently displayed on the liquid crystal. It can be used to display images of devices 5 and 6, and can brighten the screen.
複合偏光板1,2は、上記した引張弾性率の緩衝層15a,15bをそれぞれ有しているため、高温耐久試験を行った場合に外観不良が発生しにくい。これにより、複合偏光板1,又は複合偏光板2を有する液晶表示装置5,6は、高温条件下に曝された場合にも、視認性の低下を抑制することができる。
Since the composite polarizing plates 1 and 2 have the above-mentioned cushioning layers 15a and 15b having a tensile elastic modulus, respectively, appearance defects are unlikely to occur when a high temperature durability test is performed. As a result, the liquid crystal display devices 5 and 6 having the composite polarizing plate 1 or the composite polarizing plate 2 can suppress the deterioration of visibility even when exposed to high temperature conditions.
以下、上記した複合偏光板及び液晶表示装置をなす各部材の詳細について説明する。
Hereinafter, details of each member forming the above-mentioned composite polarizing plate and liquid crystal display device will be described.
〔緩衝層〕
緩衝層は、上記した範囲の引張弾性率を有するものである。緩衝層は、上記した範囲の面内レタデーションRe(590)を有することが好ましい。緩衝層は、樹脂フィルムであってもよく、硬化性成分を含む樹脂組成物の硬化物層であってもよい。 [Cushioning layer]
The buffer layer has a tensile elastic modulus in the above range. The buffer layer preferably has an in-plane retardation Re (590) in the above range. The buffer layer may be a resin film or a cured product layer of a resin composition containing a curable component.
緩衝層は、上記した範囲の引張弾性率を有するものである。緩衝層は、上記した範囲の面内レタデーションRe(590)を有することが好ましい。緩衝層は、樹脂フィルムであってもよく、硬化性成分を含む樹脂組成物の硬化物層であってもよい。 [Cushioning layer]
The buffer layer has a tensile elastic modulus in the above range. The buffer layer preferably has an in-plane retardation Re (590) in the above range. The buffer layer may be a resin film or a cured product layer of a resin composition containing a curable component.
緩衝層の厚みは、20μm以上であることが好ましく、25μm以上であることがより好ましく、30μm以上であることがさらに好ましく、通常、80μm以下であり、70μm以下であってもよく、60μm以下であってもよい。
The thickness of the buffer layer is preferably 20 μm or more, more preferably 25 μm or more, further preferably 30 μm or more, and usually 80 μm or less, 70 μm or less, 60 μm or less. There may be.
〔緩衝層を構成する樹脂フィルム〕
緩衝層が樹脂フィルムである場合、樹脂フィルムを構成する樹脂材料(樹脂)は、透明性、機械的強度、熱安定性、水分遮蔽性、及び位相差値の安定性等に優れるものが好ましい。樹脂材料は、熱可塑性樹脂であることが好ましい。このような樹脂材料としては、特に限定されないが、例えば、セルロースエステル系樹脂;(メタ)アクリル酸系樹脂;鎖状脂肪族オレフィン系樹脂、環状オレフィン系樹脂等のオレフィン系樹脂;ポリ塩化ビニル系樹脂;スチレン系樹脂;アクリロニトリル・ブタジエン・スチレン系樹脂;アクリロニトリル・スチレン系樹脂;ポリ酢酸ビニル系樹脂;ポリ塩化ビニリデン系樹脂;ポリアミド系樹脂;ポリアセタール系樹脂;ポリカーボネート系樹脂;変性ポリフェニレンエーテル系樹脂;ポリブチレンテフタレート系樹脂、ポリエチレンテフタレート系樹脂等のポリエステル系樹脂;ポリスルホン系樹脂;ポリエーテルスルホン系樹脂;ポリアリレート系樹脂;ポリアミドイミド系樹脂;ポリイミド系樹脂等が挙げられ、これらのうち1種又は2種以上を組合わせて用いることができる。なかでも、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂から選ばれる樹脂を用いることが好ましい。本明細書において、「(メタ)アクリル」とは、アクリル又はメタクリルのいずれでもよいことを意味する。(メタ)アクリロイル等の「(メタ)」も同様の意味である。 [Resin film constituting the buffer layer]
When the buffer layer is a resin film, the resin material (resin) constituting the resin film is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, and the like. The resin material is preferably a thermoplastic resin. Such a resin material is not particularly limited, and is, for example, a cellulose ester resin; a (meth) acrylic acid resin; an olefin resin such as a chain aliphatic olefin resin or a cyclic olefin resin; a polyvinyl chloride resin. Resin; styrene resin; acrylonitrile / butadiene / styrene resin; acrylonitrile / styrene resin; polyvinyl acetate resin; polyvinylidene chloride resin; polyamide resin; polyacetal resin; polycarbonate resin; modified polyphenylene ether resin; Polybutylene teflate-based resin, polyester-based resin such as polyethylene teftalate-based resin; polysulfone-based resin; polyether sulfone-based resin; polyarylate-based resin; polyamideimide-based resin; polyimide-based resin, etc. Species or a combination of two or more species can be used. Among them, it is preferable to use a resin selected from a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. As used herein, the term "(meth) acrylic" means that it may be either acrylic or methacryl. (Meta) "(Meta)" such as acryloyl has the same meaning.
緩衝層が樹脂フィルムである場合、樹脂フィルムを構成する樹脂材料(樹脂)は、透明性、機械的強度、熱安定性、水分遮蔽性、及び位相差値の安定性等に優れるものが好ましい。樹脂材料は、熱可塑性樹脂であることが好ましい。このような樹脂材料としては、特に限定されないが、例えば、セルロースエステル系樹脂;(メタ)アクリル酸系樹脂;鎖状脂肪族オレフィン系樹脂、環状オレフィン系樹脂等のオレフィン系樹脂;ポリ塩化ビニル系樹脂;スチレン系樹脂;アクリロニトリル・ブタジエン・スチレン系樹脂;アクリロニトリル・スチレン系樹脂;ポリ酢酸ビニル系樹脂;ポリ塩化ビニリデン系樹脂;ポリアミド系樹脂;ポリアセタール系樹脂;ポリカーボネート系樹脂;変性ポリフェニレンエーテル系樹脂;ポリブチレンテフタレート系樹脂、ポリエチレンテフタレート系樹脂等のポリエステル系樹脂;ポリスルホン系樹脂;ポリエーテルスルホン系樹脂;ポリアリレート系樹脂;ポリアミドイミド系樹脂;ポリイミド系樹脂等が挙げられ、これらのうち1種又は2種以上を組合わせて用いることができる。なかでも、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂から選ばれる樹脂を用いることが好ましい。本明細書において、「(メタ)アクリル」とは、アクリル又はメタクリルのいずれでもよいことを意味する。(メタ)アクリロイル等の「(メタ)」も同様の意味である。 [Resin film constituting the buffer layer]
When the buffer layer is a resin film, the resin material (resin) constituting the resin film is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, and the like. The resin material is preferably a thermoplastic resin. Such a resin material is not particularly limited, and is, for example, a cellulose ester resin; a (meth) acrylic acid resin; an olefin resin such as a chain aliphatic olefin resin or a cyclic olefin resin; a polyvinyl chloride resin. Resin; styrene resin; acrylonitrile / butadiene / styrene resin; acrylonitrile / styrene resin; polyvinyl acetate resin; polyvinylidene chloride resin; polyamide resin; polyacetal resin; polycarbonate resin; modified polyphenylene ether resin; Polybutylene teflate-based resin, polyester-based resin such as polyethylene teftalate-based resin; polysulfone-based resin; polyether sulfone-based resin; polyarylate-based resin; polyamideimide-based resin; polyimide-based resin, etc. Species or a combination of two or more species can be used. Among them, it is preferable to use a resin selected from a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin. As used herein, the term "(meth) acrylic" means that it may be either acrylic or methacryl. (Meta) "(Meta)" such as acryloyl has the same meaning.
樹脂フィルムを構成する樹脂材料は、任意の適切なポリマー変性を行ってから用いることもでき、このポリマー変性としては、例えば、共重合、架橋、分子末端、立体規則性制御、及び異種ポリマー同士の反応を伴う場合を含む混合等の変性が挙げられる。
The resin material constituting the resin film can be used after performing any appropriate polymer modification, and the polymer modification includes, for example, copolymerization, cross-linking, molecular terminalization, stereoregularity control, and dissimilar polymers. Modifications such as mixing, including cases involving a reaction, can be mentioned.
セルロースエステル系樹脂は、綿花リンタや木材パルプ(広葉樹パルプ、針葉樹パルプ)等の原料セルロースから得られるセルロースの水酸基における水素原子の一部又は全部がアセチル基、プロピオニル基及び/又はブチリル基で置換された、セルロース有機酸エステル又はセルロース混合有機酸エステルである。例えば、セルロースの酢酸エステル、プロピオン酸エステル、酪酸エステル、及びそれらの混合エステル等からなるものが挙げられる。中でも、トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネート、及びセルロースアセテートブチレート等が好ましい。
In the cellulose ester-based resin, a part or all of hydrogen atoms in the hydroxyl group of cellulose obtained from raw material cellulose such as cotton linter and wood pulp (perforated tree pulp, coniferous tree pulp) are replaced with acetyl group, propionyl group and / or butyryl group. In addition, it is a cellulose organic acid ester or a cellulose mixed organic acid ester. For example, those composed of acetic acid ester of cellulose, propionic acid ester, butyric acid ester, mixed ester thereof and the like can be mentioned. Among them, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
(メタ)アクリル酸系樹脂は、(メタ)アクリロイル基を有する化合物を主な構成モノマーとする樹脂である。(メタ)アクリル系樹脂の具体例は、例えば、ポリメタクリル酸メチル等のポリ(メタ)アクリル酸エステル;メタクリル酸メチル-(メタ)アクリル酸共重合体;メタクリル酸メチル-(メタ)アクリル酸エステル共重合体;メタクリル酸メチル-アクリル酸エステル-(メタ)アクリル酸共重合体;(メタ)アクリル酸メチル-スチレン共重合体(MS樹脂等);メタクリル酸メチル-メタクリル酸シクロヘキシル共重合体、メタクリル酸メチル-(メタ)アクリル酸ノルボルニル共重合体等のメタクリル酸メチルと脂環族炭化水素基を有する化合物との共重合体等を含む。好ましくは、ポリ(メタ)アクリル酸メチル等のポリ(メタ)アクリル酸C1-6アルキルエステルを主成分とする重合体が用いられ、より好ましくはメタクリル酸メチルを主成分(50~100重量%、好ましくは70~100重量%)とするメタクリル酸メチル系樹脂が用いられる。
The (meth) acrylic acid-based resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer. Specific examples of the (meth) acrylic resin include poly (meth) acrylic acid esters such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymers; methyl methacrylate- (meth) acrylic acid esters. Copolymers: Methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer; (meth) methyl acrylate-styrene copolymer (MS resin, etc.); methyl methacrylate-cyclohexyl methacrylate copolymer, methacryl Includes a copolymer of methyl methacrylate such as a methyl- (meth) acrylate norbornyl copolymer and a compound having an alicyclic hydrocarbon group. A polymer containing poly (meth) acrylic acid C 1-6 alkyl ester as a main component, such as methyl poly (meth) acrylate, is preferably used, and more preferably methyl methacrylate is used as a main component (50 to 100% by weight). , Preferably 70 to 100% by weight), a methyl methacrylate-based resin is used.
(メタ)アクリル酸系樹脂は、正の複屈折を発現する構造単位を有していてもよい。正の複屈折を発現する構造単位と負の複屈折を発現する構造単位とを有していれば、その存在比を調整することにより、(メタ)アクリル酸系樹脂から形成されたフィルムの位相差を制御することができ、低位相差の(メタ)アクリル酸系樹脂フィルムを得ることができる。正の複屈折を発現する構造単位としては、例えば、ラクトン環、ポリカーボネート、ポリビニルアルコール、酢酸セルロース、ポリエステル、ポリアリレート、ポリイミド、ポリオレフィン等を構成する構造単位、後述の一般式(1)で示される構造単位が挙げられる。負の複屈折を発現する構造単位としては、例えば、スチレン系モノマー、マレイミド系モノマー等を由来とする構造単位、ポリメチルメタクリレートの構造単位、後述の一般式(3)で示される構造単位等が挙げられる。
The (meth) acrylic acid-based resin may have a structural unit that expresses positive birefringence. If it has a structural unit that expresses positive birefringence and a structural unit that expresses negative birefringence, the position of the film formed from the (meth) acrylic acid-based resin can be adjusted by adjusting the abundance ratio thereof. The phase difference can be controlled, and a (meth) acrylic acid-based resin film having a low phase difference can be obtained. As the structural unit that expresses positive birefringence, for example, a structural unit constituting a lactone ring, polycarbonate, polyvinyl alcohol, cellulose acetate, polyester, polyarylate, polyimide, polyolefin, etc., is represented by the general formula (1) described later. Structural units can be mentioned. Examples of the structural unit that expresses negative birefringence include structural units derived from styrene-based monomers, maleimide-based monomers, etc., polymethylmethacrylate structural units, structural units represented by the general formula (3) described later, and the like. Can be mentioned.
(メタ)アクリル酸系樹脂として、ラクトン環構造又はグルタルイミド構造を有する(メタ)アクリル酸系樹脂が好ましく用いられる。ラクトン環構造又はグルタルイミド構造を有する(メタ)アクリル酸系樹脂は耐熱性に優れる。より好ましくは、グルタルイミド構造を有する(メタ)アクリル酸系樹脂である。グルタルイミド構造を有する(メタ)アクリル酸系樹脂を用いれば、低透湿、かつ、位相差及び紫外線透過率の小さい(メタ)アクリル酸系樹脂フィルムを得ることができる。グルタルイミド構造を有する(メタ)アクリル酸系樹脂(以下、「グルタルイミド樹脂」とも称する)は、例えば、特開2006-309033号公報、特開2006-317560号公報、特開2006-328329号公報、特開2006-328334号公報、特開2006-337491号公報、特開2006-337492号公報、特開2006-337493号公報、特開2006-337569号公報、特開2007-9182号公報、特開2009-161744号公報に記載されている。これらの記載は、本明細書に参考として援用される。
As the (meth) acrylic acid-based resin, a (meth) acrylic acid-based resin having a lactone ring structure or a glutarimide structure is preferably used. A (meth) acrylic acid-based resin having a lactone ring structure or a glutarimide structure has excellent heat resistance. More preferably, it is a (meth) acrylic acid-based resin having a glutarimide structure. By using a (meth) acrylic acid-based resin having a glutarimide structure, a (meth) acrylic acid-based resin film having low moisture permeability and low phase difference and ultraviolet transmittance can be obtained. Examples of the (meth) acrylic acid-based resin having a glutarimide structure (hereinafter, also referred to as “glutarimide resin”) include JP-A-2006-309033, JP-A-2006-317560, and JP-A-2006-328329. , JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492, JP-A-2006-337493, JP-A-2006-337569, JP-A-2007-9182, It is described in Kai 2009-161744. These statements are incorporated herein by reference.
グルタルイミド樹脂は、好ましくは、下記一般式(1)で表される構造単位(以下、「グルタルイミド単位」とも称する)と、下記一般式(2)で表される構造単位(以下、「(メタ)アクリル酸エステル単位」とも称する)とを含む。
The glutarimide resin is preferably a structural unit represented by the following general formula (1) (hereinafter, also referred to as “glutarimide unit”) and a structural unit represented by the following general formula (2) (hereinafter, “( Meta) Also referred to as "acrylic acid ester unit").
[一般式(1)において、R1及びR2は、それぞれ独立して、水素又は炭素数1~8のアルキル基であり、R3は、水素、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、又は炭素数5~15の芳香環を含む置換基である。
一般式(2)において、R4及びR5は、それぞれ独立して、水素又は炭素数1~8のアルキル基であり、R6は、水素、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、又は炭素数5~15の芳香環を含む置換基である。]
[In the general formula (1), R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. It is a substituent containing 3 to 12 cycloalkyl groups or an aromatic ring having 5 to 15 carbon atoms.
In the general formula (2), R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 is hydrogen, an alkyl group having 1 to 18 carbon atoms, and 3 carbon atoms. It is a substituent containing a cycloalkyl group of up to 12 or an aromatic ring having 5 to 15 carbon atoms. ]
グルタルイミド樹脂は、必要に応じて、下記一般式(3)で表される構造単位(以下、「芳香族ビニル単位」とも称する)をさらに含んでいてもよい。
The glutarimide resin may further contain a structural unit represented by the following general formula (3) (hereinafter, also referred to as “aromatic vinyl unit”), if necessary.
[一般式(3)において、R7は、水素又は炭素数1~8のアルキル基であり、R8は、炭素数6~10のアリール基である]。
[In the general formula (3), R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 is an aryl group having 6 to 10 carbon atoms].
上記一般式(1)において、好ましくは、R1及びR2は、それぞれ独立して、水素又はメチル基であり、R3は水素、メチル基、ブチル基、又はシクロヘキシル基であり、さらに好ましくは、R1はメチル基であり、R2は水素であり、R3はメチル基である。
In the above general formula (1), preferably, R 1 and R 2 are independently hydrogen or methyl groups, and R 3 is hydrogen, methyl group, butyl group, or cyclohexyl group, and more preferably. , R 1 is a methyl group, R 2 is a hydrogen, and R 3 is a methyl group.
上記グルタルイミド樹脂は、グルタルイミド単位として、単一の種類のみを含んでいてもよいし、上記一般式(1)におけるR1、R2、及びR3が異なる複数の種類を含んでいてもよい。
The glutarimide resin is a glutarimide unit, may include only a single type, R 1 in the general formula (1), R 2, and R 3 also include a plurality of different types Good.
グルタルイミド単位は、上記一般式(2)で表される(メタ)アクリル酸エステル単位をイミド化することにより、形成することができる。また、グルタルイミド単位は、無水マレイン酸等の酸無水物、又は、このような酸無水物と炭素数1~20の直鎖又は分岐のアルコールとのハーフエステル;アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、クロトン酸、フマル酸、シトラコン酸等のα,β-エチレン性不飽和カルボン酸等をイミド化することによっても、形成することができる。
The glutarimide unit can be formed by imidizing the (meth) acrylic acid ester unit represented by the above general formula (2). The glutarimide unit is an acid anhydride such as maleic anhydride, or a half ester of such an acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms; crotonic acid, methacrylic acid, maleic acid. It can also be formed by imidizing α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, and citraconic acid.
上記一般式(2)において、好ましくは、R4及びR5は、それぞれ独立して、水素又はメチル基であり、R6は水素又はメチル基であり、さらに好ましくは、R4は水素であり、R5はメチル基であり、R6はメチル基である。
In the above general formula (2), preferably R 4 and R 5 are independently hydrogen or methyl groups, R 6 is hydrogen or methyl group, and more preferably R 4 is hydrogen. , R 5 is a methyl group and R 6 is a methyl group.
グルタルイミド樹脂は、(メタ)アクリル酸エステル単位として、単一の種類のみを含んでいてもよいし、上記一般式(2)におけるR4、R5、及びR6が異なる複数の種類を含んでいてもよい。
Glutarimide resin as (meth) acrylic acid ester unit, may include only a single type, include R 4, R 5, and a plurality of types of R 6 are different in the above general formula (2) You may be.
グルタルイミド樹脂は、上記一般式(3)で表される芳香族ビニル単位として、好ましくはスチレン、α-メチルスチレン等を含み、さらに好ましくはスチレンを含む。このような芳香族ビニル単位を有するグルタルイミド樹脂を用いることにより、グルタルイミド構造の正の複屈折性を低減し、より低位相差の(メタ)アクリル系樹脂フィルムを得ることができる。
The glutarimide resin preferably contains styrene, α-methylstyrene and the like as the aromatic vinyl unit represented by the above general formula (3), and more preferably contains styrene. By using such a glutarimide resin having an aromatic vinyl unit, the positive birefringence of the glutarimide structure can be reduced, and a (meth) acrylic resin film having a lower phase difference can be obtained.
グルタルイミド樹脂は、芳香族ビニル単位として、単一の種類のみを含んでいてもよいし、上記一般式(3)におけるR7及びR8が異なる複数の種類を含んでいてもよい。
The glutarimide resin may contain only a single type as the aromatic vinyl unit, or may contain a plurality of types in which R 7 and R 8 in the above general formula (3) are different.
グルタルイミド樹脂におけるグルタルイミド単位の含有量は、例えばR3の構造等に応じて変化させることが好ましい。グルタルイミド単位の含有量は、グルタルイミド樹脂の総構造単位を基準として、好ましくは1重量%~80重量%であり、より好ましくは1重量%~70重量%であり、さらに好ましくは1重量%~60重量%であり、特に好ましくは1重量%~50重量%である。グルタルイミド単位の含有量がこのような範囲であれば、耐熱性に優れた低位相差の(メタ)アクリル系樹脂フィルムが得られ得る。
The content of the glutarimide unit in glutarimide resin is preferably, for example, vary depending on the structure and the like of R 3. The content of the glutarimide unit is preferably 1% by weight to 80% by weight, more preferably 1% by weight to 70% by weight, still more preferably 1% by weight, based on the total structural unit of the glutarimide resin. It is about 60% by weight, and particularly preferably 1% by weight to 50% by weight. When the content of the glutarimide unit is in such a range, a low phase difference (meth) acrylic resin film having excellent heat resistance can be obtained.
グルタルイミド樹脂における芳香族ビニル単位の含有量は、目的や要求される特性に応じて適切に設定され得る。用途によっては、芳香族ビニル単位の含有量は0であってもよい。芳香族ビニル単位が含まれる場合、その含有量は、グルタルイミド樹脂のグルタルイミド単位を基準として、好ましくは10重量%~80重量%であり、より好ましくは20重量%~80重量%であり、さらに好ましくは20重量%~60重量%であり、特に好ましくは20重量%~50重量%である。芳香族ビニル単位の含有量がこのような範囲であれば、低位相差、かつ、耐熱性及び機械的強度に優れた(メタ)アクリル酸系樹脂フィルムが得られ得る。
The content of the aromatic vinyl unit in the glutarimide resin can be appropriately set according to the purpose and required properties. Depending on the application, the content of the aromatic vinyl unit may be zero. When the aromatic vinyl unit is contained, the content thereof is preferably 10% by weight to 80% by weight, more preferably 20% by weight to 80% by weight, based on the glutarimide unit of the glutarimide resin. It is more preferably 20% by weight to 60% by weight, and particularly preferably 20% by weight to 50% by weight. When the content of the aromatic vinyl unit is in such a range, a (meth) acrylic acid-based resin film having a low phase difference and excellent heat resistance and mechanical strength can be obtained.
グルタルイミド樹脂には、必要に応じて、グルタルイミド単位、(メタ)アクリル酸エステル単位、及び芳香族ビニル単位以外のその他の構造単位がさらに共重合されていてもよい。その他の構造単位としては、例えば、アクリロニトリルやメタクリロニトリル等のニトリル系単量体;マレイミド、N-メチルマレイミド、N-フェニルマレイミド、N-シクロヘキシルマレイミド等のマレイミド系単量体から構成される構造単位が挙げられる。これらのその他の構造単位は、グルタルイミド樹脂中に、直接共重合していてもよいし、グラフト共重合していてもよい。
If necessary, the glutarimide resin may be further copolymerized with other structural units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit. Other structural units include, for example, a structure composed of nitrile-based monomers such as acrylonitrile and methacrylonitrile; maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. The unit is mentioned. These other structural units may be directly copolymerized or graft-copolymerized in the glutarimide resin.
オレフィン系樹脂は、エチレン及びプロピレン等の鎖状脂肪族オレフィン、又はノルボルネンやその置換体(以下、これらを総称してノルボルネン系モノマーとも称する)等の脂環式オレフィンから誘導される構成単位からなる樹脂である。オレフィン系樹脂は、2種以上のモノマーを用いた共重合体であってもよい。
The olefin-based resin is composed of a structural unit derived from a chain aliphatic olefin such as ethylene and propylene, or an alicyclic olefin such as norbornene or a substitute thereof (hereinafter, these are collectively referred to as a norbornene-based monomer). It is a resin. The olefin resin may be a copolymer using two or more kinds of monomers.
オレフィン系樹脂としては、脂環式オレフィンから誘導される構成単位を主に含む樹脂である環状オレフィン系樹脂が好ましく用いられる。環状オレフィン系樹脂を構成する脂環式オレフィンの典型的な例としては、ノルボルネン系モノマー等を挙げることができる。ノルボルネンとは、ノルボルナンの1つの炭素-炭素結合が二重結合となった化合物であって、IUPAC命名法によれば、ビシクロ[2,2,1]ヘプト-2-エンと命名されるものである。ノルボルネンの置換体の例としては、ノルボルネンの二重結合位置を1,2-位として、3-置換体、4-置換体、及び4,5-ジ置換体等を挙げることができ、さらにはジシクロペンタジエンやジメタノオクタヒドロナフタレン等も挙げることができる。
As the olefin resin, a cyclic olefin resin which is a resin mainly containing a constituent unit derived from an alicyclic olefin is preferably used. Typical examples of the alicyclic olefin constituting the cyclic olefin resin include norbornene-based monomers. Norbornene is a compound in which one carbon-carbon bond of norbornane is a double bond, and is named bicyclo [2,2,1] hept-2-ene according to the IUPAC nomenclature. is there. Examples of the substitution product of norbornene include 3-substituted product, 4-substituted product, 4,5-di-substituted product, etc., with the double bond position of norbornene at the 1,2-position, and further. Dicyclopentadiene, dimethanooctahydronaphthalene and the like can also be mentioned.
環状オレフィン系樹脂は、その構成単位にノルボルナン環を有していてもよいし、有していなくてもよい。構成単位にノルボルナン環を有さない環状オレフィン系樹脂を形成するノルボルネン系モノマーとしては、たとえば、開環により5員環となるもの、代表的には、ノルボルネン、ジシクロペンタジエン、1-又は4-メチルノルボルネン、及び4-フェニルノルボルネン等が挙げられる。環状オレフィン系樹脂が共重合体である場合、その分子の配列状態は特に限定されるものではなく、ランダム共重合体であってもよいし、ブロック共重合体であってもよいし、グラフト共重合体であってもよい。
The cyclic olefin resin may or may not have a norbornane ring as its constituent unit. Examples of the norbornene-based monomer forming a cyclic olefin-based resin having no norbornene ring as a constituent unit include those having a 5-membered ring by ring-opening, typically norbornene, dicyclopentadiene, 1- or 4-. Examples thereof include methylnorbornene and 4-phenylnorbornene. When the cyclic olefin-based resin is a copolymer, the arrangement state of the molecule is not particularly limited, and it may be a random copolymer, a block copolymer, or a graft. It may be a polymer.
環状オレフィン系樹脂のより具体的な例としては、例えば、ノルボルネン系モノマーの開環重合体、ノルボルネン系モノマーと他のモノマーとの開環共重合体、それらにマレイン酸付加やシクロペンタジエン付加等がなされたポリマー変性物、及びこれらを水素添加した重合体又は共重合体;ノルボルネン系モノマーの付加重合体、及びノルボルネン系モノマーと他のモノマーとの付加共重合体等が挙げられる。共重合体とする場合における他のモノマーとしては、α-オレフィン類、シクロアルケン類、及び非共役ジエン類等が挙げられる。また、環状オレフィン系樹脂は、ノルボルネン系モノマー及び他の脂環式オレフィンの1種又は2種以上を用いた共重合体であってもよい。
More specific examples of the cyclic olefin resin include, for example, a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer, and addition of maleic acid and cyclopentadiene to them. Examples thereof include polymer modified products made, and polymers or copolymers obtained by hydrogenating them; addition polymers of norbornene-based monomers, and addition copolymers of norbornene-based monomers and other monomers. Examples of other monomers used as copolymers include α-olefins, cycloalkenes, non-conjugated dienes and the like. Further, the cyclic olefin resin may be a copolymer using one or more of norbornene-based monomers and other alicyclic olefins.
環状オレフィン系樹脂としては、ノルボルネン系モノマーを用いた開環重合体又は開環共重合体に水素添加した樹脂が好ましく用いられる。
As the cyclic olefin resin, a ring-opening polymer using a norbornene-based monomer or a resin obtained by hydrogenating a ring-opening copolymer is preferably used.
上記した樹脂フィルムを構成する樹脂材料は、透明性を損なわない範囲で、適宜の添加物が配合されていてもよい。添加物として例えば、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、造核剤、防曇剤、アンチブロッキング剤、位相差低減剤、安定剤、加工助剤、可塑剤、耐衝撃助剤、艶消し剤、抗菌剤、防かび剤等を挙げることができる。これらの添加物は、複数種が併用されてもよい。
The resin material constituting the above-mentioned resin film may contain an appropriate additive as long as the transparency is not impaired. Additives include, for example, antioxidants, UV absorbers, antistatic agents, lubricants, nucleating agents, antifogging agents, antiblocking agents, phase difference reducing agents, stabilizers, processing aids, plasticizers, impact resistant aids. , Matters, antibacterial agents, antifungal agents and the like. A plurality of kinds of these additives may be used in combination.
上記した樹脂材料を用いて樹脂フィルムを製膜する方法としては、任意の最適な方法を適宜選択すればよい。例えば、溶剤に溶解させた樹脂を、金属製のバンド又はドラムに流延し、溶剤を乾燥除去してフィルムを得る溶剤キャスト法、樹脂をその溶融温度以上に加熱し、混練してダイから押し出し、冷却することによりフィルムを得る溶融押出法等が挙げられる。溶融押出法では、単層フィルムを押し出すこともできるし、多層フィルムを同時押出することもできる。
As a method for forming a resin film using the above-mentioned resin material, any optimum method may be appropriately selected. For example, a solvent casting method in which a resin dissolved in a solvent is cast on a metal band or drum and the solvent is dried and removed to obtain a film. The resin is heated above its melting temperature, kneaded and extruded from a die. , A melt extrusion method for obtaining a film by cooling, and the like. In the melt extrusion method, a single-layer film can be extruded, or a multilayer film can be extruded at the same time.
上記したように、樹脂フィルムは、延伸加工が施された延伸フィルムであってもよい。
延伸加工を施すことにより、引張弾性率を所望の範囲に調整してもよい。延伸処理としては、一軸延伸や二軸延伸等が挙げられる。 As described above, the resin film may be a stretched film that has been stretched.
The tensile elastic modulus may be adjusted to a desired range by performing a stretching process. Examples of the stretching treatment include uniaxial stretching and biaxial stretching.
延伸加工を施すことにより、引張弾性率を所望の範囲に調整してもよい。延伸処理としては、一軸延伸や二軸延伸等が挙げられる。 As described above, the resin film may be a stretched film that has been stretched.
The tensile elastic modulus may be adjusted to a desired range by performing a stretching process. Examples of the stretching treatment include uniaxial stretching and biaxial stretching.
〔緩衝層を構成する硬化性成分を含む樹脂組成物の硬化物層〕
緩衝層が硬化性成分を含む樹脂組成物の硬化物層である場合、樹脂組成物に含まれる硬化性成分は、活性エネルギー線の照射により硬化する活性エネルギー線硬化性化合物、又は、加熱により硬化する熱硬化性硬化物であることが好ましい。硬化性成分は、活性エネルギー線硬化性化合物であることがより好ましい。 [Cured product layer of resin composition containing curable components constituting the buffer layer]
When the buffer layer is a cured product layer of a resin composition containing a curable component, the curable component contained in the resin composition is an active energy ray-curable compound that is cured by irradiation with active energy rays, or a cured product by heating. It is preferably a thermosetting cured product. The curable component is more preferably an active energy ray-curable compound.
緩衝層が硬化性成分を含む樹脂組成物の硬化物層である場合、樹脂組成物に含まれる硬化性成分は、活性エネルギー線の照射により硬化する活性エネルギー線硬化性化合物、又は、加熱により硬化する熱硬化性硬化物であることが好ましい。硬化性成分は、活性エネルギー線硬化性化合物であることがより好ましい。 [Cured product layer of resin composition containing curable components constituting the buffer layer]
When the buffer layer is a cured product layer of a resin composition containing a curable component, the curable component contained in the resin composition is an active energy ray-curable compound that is cured by irradiation with active energy rays, or a cured product by heating. It is preferably a thermosetting cured product. The curable component is more preferably an active energy ray-curable compound.
〔A〕活性エネルギー線硬化性化合物を含む樹脂組成物
活性エネルギー線硬化性化合物としては、電子線硬化性化合物、紫外線硬化性化合物、又は可視光線硬化性化合物が挙げられる。このうち、紫外線硬化性化合物又は可視光線硬化性化合物であることが好ましく、紫外線硬化性化合物がより好ましい。紫外線硬化性化合物又は可視光線硬化性化合物を含む樹脂組成物は、ラジカル重合型樹脂組成物であってもよく、カチオン重合型樹脂組成物であってもよい。本明細書において、紫外線とは、波長10nm以上380nm未満の範囲の活性エネルギー線をいい、可視光線とは、波長380nm以上800nm以下の活性エネルギー線をいう。 [A] Resin Composition Containing Active Energy Ray Curable Compound Examples of the active energy ray curable compound include an electron beam curable compound, an ultraviolet curable compound, and a visible light curable compound. Of these, an ultraviolet curable compound or a visible light curable compound is preferable, and an ultraviolet curable compound is more preferable. The resin composition containing the ultraviolet curable compound or the visible light curable compound may be a radical polymerization type resin composition or a cationic polymerization type resin composition. In the present specification, ultraviolet rays refer to active energy rays having a wavelength in the range of 10 nm or more and less than 380 nm, and visible light means active energy rays having a wavelength of 380 nm or more and 800 nm or less.
活性エネルギー線硬化性化合物としては、電子線硬化性化合物、紫外線硬化性化合物、又は可視光線硬化性化合物が挙げられる。このうち、紫外線硬化性化合物又は可視光線硬化性化合物であることが好ましく、紫外線硬化性化合物がより好ましい。紫外線硬化性化合物又は可視光線硬化性化合物を含む樹脂組成物は、ラジカル重合型樹脂組成物であってもよく、カチオン重合型樹脂組成物であってもよい。本明細書において、紫外線とは、波長10nm以上380nm未満の範囲の活性エネルギー線をいい、可視光線とは、波長380nm以上800nm以下の活性エネルギー線をいう。 [A] Resin Composition Containing Active Energy Ray Curable Compound Examples of the active energy ray curable compound include an electron beam curable compound, an ultraviolet curable compound, and a visible light curable compound. Of these, an ultraviolet curable compound or a visible light curable compound is preferable, and an ultraviolet curable compound is more preferable. The resin composition containing the ultraviolet curable compound or the visible light curable compound may be a radical polymerization type resin composition or a cationic polymerization type resin composition. In the present specification, ultraviolet rays refer to active energy rays having a wavelength in the range of 10 nm or more and less than 380 nm, and visible light means active energy rays having a wavelength of 380 nm or more and 800 nm or less.
〔A1〕ラジカル重合型樹脂組成物
ラジカル重合型樹脂組成物は、硬化性成分としてラジカル重合性化合物を含む。ラジカル重合性化合物は、(メタ)アクリロイル基、ビニル基等の炭素-炭素二重結合のラジカル重合性の官能基を有する化合物が挙げられる。ラジカル重合性化合物は、単官能ラジカル重合性化合物又は二官能以上の多官能ラジカル重合性化合物のいずれも用いることができる。ラジカル重合性化合物は、1種を単独で、又は2種以上を組み合わせて用いることができる。ラジカル重合性化合物としては、例えば、(メタ)アクリロイル基を有する化合物が好適である。 [A1] Radical Polymerizable Resin Composition The radically polymerizable resin composition contains a radically polymerizable compound as a curable component. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As the radically polymerizable compound, either a monofunctional radically polymerizable compound or a bifunctional or higher functional radically polymerizable compound can be used. The radically polymerizable compound may be used alone or in combination of two or more. As the radically polymerizable compound, for example, a compound having a (meth) acryloyl group is suitable.
ラジカル重合型樹脂組成物は、硬化性成分としてラジカル重合性化合物を含む。ラジカル重合性化合物は、(メタ)アクリロイル基、ビニル基等の炭素-炭素二重結合のラジカル重合性の官能基を有する化合物が挙げられる。ラジカル重合性化合物は、単官能ラジカル重合性化合物又は二官能以上の多官能ラジカル重合性化合物のいずれも用いることができる。ラジカル重合性化合物は、1種を単独で、又は2種以上を組み合わせて用いることができる。ラジカル重合性化合物としては、例えば、(メタ)アクリロイル基を有する化合物が好適である。 [A1] Radical Polymerizable Resin Composition The radically polymerizable resin composition contains a radically polymerizable compound as a curable component. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As the radically polymerizable compound, either a monofunctional radically polymerizable compound or a bifunctional or higher functional radically polymerizable compound can be used. The radically polymerizable compound may be used alone or in combination of two or more. As the radically polymerizable compound, for example, a compound having a (meth) acryloyl group is suitable.
(単官能ラジカル重合性化合物)
単官能ラジカル重合性化合物としては、例えば、(メタ)アクリルアミド基を有する(メタ)アクリルアミド誘導体が挙げられる。(メタ)アクリルアミド誘導体は、輝度向上フィルムと硬化物層との接着性を確保する上で、また、重合速度が速く生産性に優れる点で好ましい。(メタ)アクリルアミド誘導体の具体例としては、例えば、N-メチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-ヘキシル(メタ)アクリルアミド等のN-アルキル基含有(メタ)アクリルアミド誘導体;N-メチロール(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミド、N-メチロール-N-プロパン(メタ)アクリルアミド等のN-ヒドロキシアルキル基含有(メタ)アクリルアミド誘導体;アミノメチル(メタ)アクリルアミド、アミノエチル(メタ)アクリルアミド等のN-アミノアルキル基含有(メタ)アクリルアミド誘導体;N-メトキシメチルアクリルアミド、N-エトキシメチルアクリルアミド等のN-アルコキシ基含有(メタ)アクリルアミド誘導体;メルカプトメチル(メタ)アクリルアミド、メルカプトエチル(メタ)アクリルアミド等のN-メルカプトアルキル基含有(メタ)アクリルアミド誘導体等が挙げられる。(メタ)アクリルアミド基の窒素原子が複素環を形成している複素環含有(メタ)アクリルアミド誘導体としては、例えば、N-アクリロイルモルホリン、N-アクリロイルピペリジン、N-メタクリロイルピペリジン、N-アクリロイルピロリジン等が挙げられる。 (Monofunctional radical polymerizable compound)
Examples of the monofunctional radically polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group. The (meth) acrylamide derivative is preferable in terms of ensuring the adhesiveness between the brightness-improving film and the cured product layer, and also in terms of high polymerization rate and excellent productivity. Specific examples of the (meth) acrylamide derivative include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N. -N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N- N-Hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide can be mentioned. .. Examples of the heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle include N-acrylloylmorpholine, N-acrylloylpiperidin, N-methacryloylpiperidin, and N-acrylloylpyrolidin. Can be mentioned.
単官能ラジカル重合性化合物としては、例えば、(メタ)アクリルアミド基を有する(メタ)アクリルアミド誘導体が挙げられる。(メタ)アクリルアミド誘導体は、輝度向上フィルムと硬化物層との接着性を確保する上で、また、重合速度が速く生産性に優れる点で好ましい。(メタ)アクリルアミド誘導体の具体例としては、例えば、N-メチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-ヘキシル(メタ)アクリルアミド等のN-アルキル基含有(メタ)アクリルアミド誘導体;N-メチロール(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミド、N-メチロール-N-プロパン(メタ)アクリルアミド等のN-ヒドロキシアルキル基含有(メタ)アクリルアミド誘導体;アミノメチル(メタ)アクリルアミド、アミノエチル(メタ)アクリルアミド等のN-アミノアルキル基含有(メタ)アクリルアミド誘導体;N-メトキシメチルアクリルアミド、N-エトキシメチルアクリルアミド等のN-アルコキシ基含有(メタ)アクリルアミド誘導体;メルカプトメチル(メタ)アクリルアミド、メルカプトエチル(メタ)アクリルアミド等のN-メルカプトアルキル基含有(メタ)アクリルアミド誘導体等が挙げられる。(メタ)アクリルアミド基の窒素原子が複素環を形成している複素環含有(メタ)アクリルアミド誘導体としては、例えば、N-アクリロイルモルホリン、N-アクリロイルピペリジン、N-メタクリロイルピペリジン、N-アクリロイルピロリジン等が挙げられる。 (Monofunctional radical polymerizable compound)
Examples of the monofunctional radically polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group. The (meth) acrylamide derivative is preferable in terms of ensuring the adhesiveness between the brightness-improving film and the cured product layer, and also in terms of high polymerization rate and excellent productivity. Specific examples of the (meth) acrylamide derivative include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N. -N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N- N-Hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide can be mentioned. .. Examples of the heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle include N-acrylloylmorpholine, N-acrylloylpiperidin, N-methacryloylpiperidin, and N-acrylloylpyrolidin. Can be mentioned.
(メタ)アクリルアミド誘導体のなかでも、輝度向上フィルムに直接接するように硬化物層を設ける場合には、接着性の点から、N-ヒドロキシアルキル基含有(メタ)アクリルアミド誘導体が好ましく、特に、N-ヒドロキシエチル(メタ)アクリルアミドが好ましい。
Among the (meth) acrylamide derivatives, when the cured product layer is provided so as to be in direct contact with the brightness improving film, an N-hydroxyalkyl group-containing (meth) acrylamide derivative is preferable from the viewpoint of adhesiveness, and N-hydroxyalkyl group-containing (meth) acrylamide derivative is particularly preferable. Hydroxyethyl (meth) acrylamide is preferred.
単官能ラジカル重合性化合物としては、例えば、(メタ)アクリロイルオキシ基を有する各種の(メタ)アクリル酸誘導体が挙げられる。例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、2-メチル-2-ニトロプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、s-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、t-ペンチル(メタ)アクリレート、3-ペンチル(メタ)アクリレート、2,2-ジメチルブチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、セチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、4-メチル-2-プロピルペンチル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート等の(メタ)アクリル酸(炭素数1~20)アルキルエステル類が挙げられる。
Examples of the monofunctional radically polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl. (Meta) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethyl Butyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl (meth) acrylate, n -Examples include (meth) acrylic acid (1 to 20 carbon atoms) alkyl esters such as octadecyl (meth) acrylate.
(メタ)アクリル酸誘導体としては、例えば、シクロヘキシル(メタ)アクリレート、シクロペンチル(メタ)アクリレート等のシクロアルキル(メタ)アクリレート;ベンジル(メタ)アクリレート等のアラルキル(メタ)アクリレート;2-イソボルニル(メタ)アクリレート、2-ノルボルニルメチル(メタ)アクリレート、5-ノルボルネン-2-イル-メチル(メタ)アクリレート、3-メチル-2-ノルボルニルメチル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレ-ト、ジシクロペンテニルオキシエチル(メタ)アクリレ-ト、ジシクロペンタニル(メタ)アクリレ-ト等の多環式(メタ)アクリレート;2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-メトキシメトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、アルキルフェノキシポリエチレングリコール(メタ)アクリレート等のアルコキシ基又はフェノキシ基含有(メタ)アクリレート等が挙げられる。
Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (meth). Acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) acrylice Polycyclic (meth) acrylates such as to, dicyclopentenyloxyethyl (meth) acrylicate, dicyclopentanyl (meth) acrylicate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) An alkoxy group such as acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, or phenoxy. Group-containing (meth) acrylate and the like can be mentioned.
(メタ)アクリル酸誘導体としては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、12-ヒドロキシラウリル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート;[4-(ヒドロキシメチル)シクロヘキシル]メチルアクリレート、シクロヘキサンジメタノールモノ(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート等の水酸基含有(メタ)アクリレート;グリシジル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル等のエポキシ基含有(メタ)アクリレート;2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,2-トリフルオロエチルエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、ヘキサフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート、ヘプタデカフルオロデシル(メタ)アクリレート、3-クロロ-2-ヒドロキシプロピル(メタ)アクリレート等のハロゲン含有(メタ)アクリレート;ジメチルアミノエチル(メタ)アクリレート等のアルキルアミノアルキル(メタ)アクリレート;3-オキセタニルメチル(メタ)アクリレート、3-メチルーオキセタニルメチル(メタ)アクリレート、3-エチルーオキセタニルメチル(メタ)アクリレート、3-ブチルーオキセタニルメチル(メタ)アクリレート、3-ヘキシルーオキセタニルメチル(メタ)アクリレート等のオキセタン基含有(メタ)アクリレート;テトラヒドロフルフリル(メタ)アクリレート、ブチロラクトン(メタ)アクリレート等の複素環を有する(メタ)アクリレート;ヒドロキシピバリン酸ネオペンチルグリコール(メタ)アクリル酸付加物;p-フェニルフェノール(メタ)アクリレート等が挙げられる。
Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as meta) acrylates, 6-hydroxyhexyl (meth) acrylates, 8-hydroxyoctyl (meth) acrylates, 10-hydroxydecyl (meth) acrylates, 12-hydroxylauryl (meth) acrylates; [4 -(Hydroxymethyl) cyclohexyl] Methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and other hydroxyl group-containing (meth) acrylate; glycidyl (meth) acrylate, 4-hydroxybutyl (Meta) Acrylate Group-containing (meth) acrylate such as glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate; dimethyl Alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylates; 3-oxetanylmethyl (meth) acrylates, 3-methyl-oxetanylmethyl (meth) acrylates, 3-ethyl-oxetanylmethyl (meth) acrylates, 3-butylate. Oxetane group-containing (meth) acrylates such as ruoxetanyl methyl (meth) acrylate and 3-hexyl oxetanyl methyl (meth) acrylate; having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate (meth) Acrylate; Neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate; p-phenylphenol (meth) acrylate and the like can be mentioned.
単官能ラジカル重合性化合物としては、例えば、(メタ)アクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等のカルボキシル基含有モノマーが挙げられる。
Examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
単官能ラジカル重合性化合物としては、例えば、N-ビニルピロリドン、N-ビニル-ε-カプロラクタム、メチルビニルピロリドン等のラクタム系ビニルモノマー;ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン等の窒素含有複素環を有するビニル系モノマー等が挙げられる。
Examples of the monofunctional radically polymerizable compound include lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, and vinylpyrrole. , Vinyl imidazole, vinyl oxazole, vinyl morpholin, and other vinyl-based monomers having a nitrogen-containing heterocycle.
単官能ラジカル重合性化合物としては、例えば、活性メチレン基を有するラジカル重合性化合物を用いることができる。活性メチレン基を有するラジカル重合性化合物は、末端又は分子中に(メタ)アクリル基等の活性二重結合基を有し、かつ活性メチレン基を有する化合物である。活性メチレン基としては、例えばアセトアセチル基、アルコキシマロニル基、又はシアノアセチル基等が挙げられ、活性メチレン基はアセトアセチル基であることが好ましい。活性メチレン基を有するラジカル重合性化合物の具体例としては、例えば2-アセトアセトキシエチル(メタ)アクリレート、2-アセトアセトキシプロピル(メタ)アクリレート、2-アセトアセトキシ-1-メチルエチル(メタ)アクリレート等のアセトアセトキシアルキル(メタ)アクリレート;2-エトキシマロニルオキシエチル(メタ)アクリレート、2-シアノアセトキシエチル(メタ)アクリレート、N-(2-シアノアセトキシエチル)アクリルアミド、N-(2-プロピオニルアセトキシブチル)アクリルアミド、N-(4-アセトアセトキシメチルベンジル)アクリルアミド、N-(2-アセトアセチルアミノエチル)アクリルアミド等が挙げられる。活性メチレン基を有するラジカル重合性化合物は、アセトアセトキシアルキル(メタ)アクリレートであることが好ましい。
As the monofunctional radically polymerizable compound, for example, a radically polymerizable compound having an active methylene group can be used. A radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group at the terminal or in the molecule and having an active methylene group. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, a cyanoacetyl group and the like, and the active methylene group is preferably an acetoacetyl group. Specific examples of the radically polymerizable compound having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetacetoxy-1-methylethyl (meth) acrylate and the like. Acetoacetoxyalkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Examples thereof include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like. The radically polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
(多官能ラジカル重合性化合物)
二官能以上の多官能ラジカル重合性化合物としては、例えば、多官能(メタ)アクリルアミド誘導体であるN,N’-メチレンビス(メタ)アクリルアミド、トリプロピレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジアクリレート、2-エチル-2-ブチルプロパンジオールジ(メタ)アクリレート、ビスフェノールAジ(メタ)アクリレート、ビスフェノールAエチレンオキサイド付加物ジ(メタ)アクリレート、ビスフェノールAプロピレンオキサイド付加物ジ(メタ)アクリレート、ビスフェノールAジグリシジルエーテルジ(メタ)アクリレート、ネオぺンチルグリコールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリート、環状トリメチロールプロパンフォルマル(メタ)アクリレート、ジオキサングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、EO変性ジグリセリンテトラ(メタ)アクリレート等の(メタ)アクリル酸と多価アルコールとのエステル化物;9,9-ビス[4-(2-(メタ)アクリロイルオキシエトキシ)フェニル]フルオレン等が挙げられる。具体例としては、アロニックスM-220(東亞合成社製)、ライトアクリレート1,9ND-A(共栄社化学社製)、ライトアクリレートDGE-4A(共栄社化学社製)、ライトアクリレートDCP-A(共栄社化学社製)、SR-531(Sartomer社製)、CD-536(Sartomer社製)等が好ましい。これらの多官能(メタ)アクリルアミド誘導体を用いる場合、ラジカル重合型樹脂組成物は、必要に応じて各種のエポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレートや、各種の(メタ)アクリレート系モノマー等を含んでいてもよい。多官能(メタ)アクリルアミド誘導体は、重合速度が速く生産性に優れる上、樹脂組成物を硬化物とした場合の架橋性に優れるため、ラジカル重合型樹脂組成物に含有させることが好ましい。 (Polyfunctional radical polymerizable compound)
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N'-methylenebis (meth) acrylamide, which is a polyfunctional (meth) acrylamide derivative, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate , Bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (Meta) Acrylate, Tricyclodecanedimethanol Di (Meta) Acrylate, Cyclic Trimethylol Propaneformal (Meta) Acrylate, Dioxane Glycol Di (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate, etc. Eesterates; 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like can be mentioned. Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.),Light Acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd.). , SR-531 (manufactured by Sartomer), CD-536 (manufactured by Sartomer) and the like are preferable. When these polyfunctional (meth) acrylamide derivatives are used, the radical polymerization type resin composition may contain various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and various (meth) acrylates, if necessary. ) It may contain an acrylate-based monomer or the like. The polyfunctional (meth) acrylamide derivative is preferably contained in the radical polymerization type resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is a cured product is excellent.
二官能以上の多官能ラジカル重合性化合物としては、例えば、多官能(メタ)アクリルアミド誘導体であるN,N’-メチレンビス(メタ)アクリルアミド、トリプロピレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジアクリレート、2-エチル-2-ブチルプロパンジオールジ(メタ)アクリレート、ビスフェノールAジ(メタ)アクリレート、ビスフェノールAエチレンオキサイド付加物ジ(メタ)アクリレート、ビスフェノールAプロピレンオキサイド付加物ジ(メタ)アクリレート、ビスフェノールAジグリシジルエーテルジ(メタ)アクリレート、ネオぺンチルグリコールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリート、環状トリメチロールプロパンフォルマル(メタ)アクリレート、ジオキサングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、EO変性ジグリセリンテトラ(メタ)アクリレート等の(メタ)アクリル酸と多価アルコールとのエステル化物;9,9-ビス[4-(2-(メタ)アクリロイルオキシエトキシ)フェニル]フルオレン等が挙げられる。具体例としては、アロニックスM-220(東亞合成社製)、ライトアクリレート1,9ND-A(共栄社化学社製)、ライトアクリレートDGE-4A(共栄社化学社製)、ライトアクリレートDCP-A(共栄社化学社製)、SR-531(Sartomer社製)、CD-536(Sartomer社製)等が好ましい。これらの多官能(メタ)アクリルアミド誘導体を用いる場合、ラジカル重合型樹脂組成物は、必要に応じて各種のエポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレートや、各種の(メタ)アクリレート系モノマー等を含んでいてもよい。多官能(メタ)アクリルアミド誘導体は、重合速度が速く生産性に優れる上、樹脂組成物を硬化物とした場合の架橋性に優れるため、ラジカル重合型樹脂組成物に含有させることが好ましい。 (Polyfunctional radical polymerizable compound)
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N'-methylenebis (meth) acrylamide, which is a polyfunctional (meth) acrylamide derivative, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate , Bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (Meta) Acrylate, Tricyclodecanedimethanol Di (Meta) Acrylate, Cyclic Trimethylol Propaneformal (Meta) Acrylate, Dioxane Glycol Di (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate, etc. Eesterates; 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like can be mentioned. Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.),
ラジカル重合性化合物は、多官能ラジカル重合性化合物を含有することが、樹脂組成物の硬化物の吸水率を制御するうえで好ましい。多官能ラジカル重合性化合物のなかでも、後述するlogPow値が高いものが好ましい。
The radically polymerizable compound preferably contains a polyfunctional radically polymerizable compound in order to control the water absorption rate of the cured product of the resin composition. Among the polyfunctional radical-polymerizable compounds, those having a high logPow value, which will be described later, are preferable.
緩衝層を構成するための硬化性化合物を含む樹脂組成物は、オクタノール/水分配係数(以下、「logPow値」ということがある。)が高いものが好ましい。logPow値とは物質の親油性を表す指標であり、オクタノール/水の分配係数の対数値を意味する。logPowが高いということは親油性であることを意味し、即ち、吸水率が低いことを意味する。logPow値は測定することも可能(JIS-Z-7260記載のフラスコ浸とう法)だが、計算によって算出することもできる。本明細書では、ケンブリッジソフト社製ChemDraw Ultraで計算されたlogPow値を用いる。樹脂組成物のlogPow値は、下記式によって計算することができる。
樹脂組成物のlogPow=Σ(logPowi×Wi)
logPowi:樹脂組成物に含まれる各成分のlogPow値
Wi:(i成分のモル数)/(樹脂組成物の総モル数)
樹脂組成物のlogPow値は、好ましくは1以上、より好ましくは2以上、最も好ましくは3以上である。 The resin composition containing the curable compound for forming the buffer layer preferably has a high octanol / water partition coefficient (hereinafter, may be referred to as “logPow value”). The logPow value is an index showing the lipophilicity of a substance, and means the logarithmic value of the partition coefficient of octanol / water. A high logPow means that it is lipophilic, that is, it has a low water absorption rate. The logPow value can be measured (the flask immersion method described in JIS-Z-7260), but it can also be calculated by calculation. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft Co., Ltd. is used. The logPow value of the resin composition can be calculated by the following formula.
Resin composition logPow = Σ (logPowi × Wi)
logPower: LogPower value of each component contained in the resin composition Wi: (number of moles of i component) / (total number of moles of resin composition)
The logPow value of the resin composition is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.
樹脂組成物のlogPow=Σ(logPowi×Wi)
logPowi:樹脂組成物に含まれる各成分のlogPow値
Wi:(i成分のモル数)/(樹脂組成物の総モル数)
樹脂組成物のlogPow値は、好ましくは1以上、より好ましくは2以上、最も好ましくは3以上である。 The resin composition containing the curable compound for forming the buffer layer preferably has a high octanol / water partition coefficient (hereinafter, may be referred to as “logPow value”). The logPow value is an index showing the lipophilicity of a substance, and means the logarithmic value of the partition coefficient of octanol / water. A high logPow means that it is lipophilic, that is, it has a low water absorption rate. The logPow value can be measured (the flask immersion method described in JIS-Z-7260), but it can also be calculated by calculation. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft Co., Ltd. is used. The logPow value of the resin composition can be calculated by the following formula.
Resin composition logPow = Σ (logPowi × Wi)
logPower: LogPower value of each component contained in the resin composition Wi: (number of moles of i component) / (total number of moles of resin composition)
The logPow value of the resin composition is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.
logPow値が高いラジカル重合性化合物としては、例えば、トリシクロデカンジメタノールジ(メタ)アクリート(logPow=3.05)、イソボルニル(メタ)アクリレート(logPow=3.27)等の脂環(メタ)アクリレート;1,9-ノナンジオールジ(メタ)アクリレート(logPow=3.68)、1,10-デカンジオールジアクリレート(logPow=4.10)等の長鎖脂肪族(メタ)アクリレート;ヒドロキシピバリン酸ネオペンチルグリコール(メタ)アクリル酸付加物(logPow=3.35)、2-エチル-2-ブチルプロパンジオールジ(メタ)アクリレート(logPow=3.92)等の多分岐(メタ)アクリレート;ビスフェノールAジ(メタ)アクリレート(logPow=5.46)、ビスフェノールAエチレンオキサイド4モル付加物ジ(メタ)アクリレート(logPow=5.15)、ビスフェノールAプロピレンオキサイド2モル付加物ジ(メタ)アクリレート(logPow=6.10)、ビスフェノールAプロピレンオキサイド4モル付加物ジ(メタ)アクリレート(logPow=6.43)、9,9-ビス[4-(2-(メタ)アクリロイルオキシエトキシ)フェニル]フルオレン(logPow=7.48)、p-フェニルフェノール(メタ)アクリレート(logPow=3.98)等の芳香環を含有する(メタ)アクリレート等が挙げられる。
Examples of the radically polymerizable compound having a high logPow value include alicyclic (meth) such as tricyclodecanedimethanol di (meth) acrylate (logPow = 3.05) and isobornyl (meth) acrylate (logPow = 3.27). Acrylate; Long-chain aliphatic (meth) acrylate such as 1,9-nonanediol di (meth) acrylate (logPow = 3.68), 1,10-decanediol diacrylate (logPow = 4.10); hydroxypivalic acid Multi-branched (meth) acrylates such as neopentyl glycol (meth) acrylic acid adduct (logPow = 3.35), 2-ethyl-2-butylpropanediol di (meth) acrylate (logPow = 3.92); bisphenol A Di (meth) acrylate (logPow = 5.46), bisphenol A ethylene oxide 4 mol adduct Di (meth) acrylate (logPow = 5.15), bisphenol Apropylene oxide 2 mol adduct Di (meth) acrylate (logPow =) 6.10), bisphenol Apropylene oxide 4 mol adduct di (meth) acrylate (logPow = 6.43), 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene (logPow = 7.48), (meth) acrylate containing an aromatic ring such as p-phenylphenol (meth) acrylate (logPow = 3.98) and the like can be mentioned.
ラジカル重合性化合物は、輝度向上フィルムと硬化物層との接着性や、過酷な環境下における光学耐久性を両立させる観点から、単官能ラジカル重合性化合物と多官能ラジカル重合性化合物を併用することが好ましい。通常は、ラジカル重合性化合物100重量%に対して、単官能ラジカル重合性化合物3~80重量%と多官能ラジカル重合性化合物20~97重量%の割合で併用することが好ましい。
For the radically polymerizable compound, a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound should be used in combination from the viewpoint of achieving both the adhesiveness between the brightness improving film and the cured product layer and the optical durability in a harsh environment. Is preferable. Usually, it is preferable to use the monofunctional radical polymerizable compound in an amount of 3 to 80% by weight and the polyfunctional radical polymerizable compound in an amount of 20 to 97% by weight based on 100% by weight of the radically polymerizable compound.
(光重合開始剤)
ラジカル重合型樹脂組成物は、硬化性成分として活性エネルギー線硬化性成分を含む場合には、活性エネルギー線硬化性化合物を含む組成物として用いることができる。この場合、ラジカル重合型樹脂組成物は、光重合開始剤を含有することが好ましい。 (Photopolymerization initiator)
When the radical polymerization type resin composition contains an active energy ray-curable component as a curable component, it can be used as a composition containing an active energy ray-curable compound. In this case, the radical polymerization type resin composition preferably contains a photopolymerization initiator.
ラジカル重合型樹脂組成物は、硬化性成分として活性エネルギー線硬化性成分を含む場合には、活性エネルギー線硬化性化合物を含む組成物として用いることができる。この場合、ラジカル重合型樹脂組成物は、光重合開始剤を含有することが好ましい。 (Photopolymerization initiator)
When the radical polymerization type resin composition contains an active energy ray-curable component as a curable component, it can be used as a composition containing an active energy ray-curable compound. In this case, the radical polymerization type resin composition preferably contains a photopolymerization initiator.
ラジカル重合型樹脂組成物に含まれる光重合開始剤としては、紫外線又は可視光線によって開裂する光重合開始剤を用いることができる。このような光重合開始剤としては、例えば、ベンジル、ベンゾフェノン、ベンゾイル安息香酸、3,3’-ジメチル-4-メトキシベンゾフェノン等のベンゾフェノン系化合物;4-(2-ヒドロキシエトキシ)フェニル(2-ヒドロキシ-2-プロピル)ケトン、α-ヒドロキシ-α,α’-ジメチルアセトフェノン、2-メチル-2-ヒドロキシプロピオフェノン、α-ヒドロキシシクロヘキシルフェニルケトン等の芳香族ケトン化合物;メトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフエノン、2,2-ジエトキシアセトフェノン、2-メチル-1-[4-(メチルチオ)-フェニル]-2-モルホリノプロパン-1等のアセトフェノン系化合物;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインブチルエーテル、アニソインメチルエーテル等のベンゾインエーテル系化合物;ベンジルジメチルケタール等の芳香族ケタール系化合物;2-ナフタレンスルホニルクロリド等の芳香族スルホニルクロリド系化合物;1-フェノン-1,1-プロパンジオン-2-(o-エトキシカルボニル)オキシム等の光活性オキシム系化合物;チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジクロロチオキサントン、2,4-ジエチルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントン等のチオキサントン系化合物;カンファーキノン;ハロゲン化ケトン;アシルホスフィノキシド;アシルホスフォナート等が挙げられる。光重合開始剤のなかでも、logPow値が高いものが好ましい。光重合開始剤のlogPow値は、好ましくは2以上、より好ましくは3以上、最も好ましくは4以上である。
As the photopolymerization initiator contained in the radical polymerization type resin composition, a photopolymerization initiator that is cleaved by ultraviolet rays or visible light can be used. Examples of such a photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy). Aromatic ketone compounds such as -2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexylphenylketone; methoxyacetophenone, 2,2- Acetphenone compounds such as dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1, etc .; benzoin methyl ether, benzoin Benzophenone ether compounds such as ethyl ether, benzoin isopropyl ether, benzoin butyl ether and anisoine methyl ether; aromatic ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalene sulfonyl chloride; 1-phenone- Photoactive oxime compounds such as 1,1-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4- Examples thereof include thioxanthone compounds such as dichlorothioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone; benzophenone; halogenated ketone; acylphosphinoxide; acylphosphonate and the like. Among the photopolymerization initiators, those having a high logPow value are preferable. The logPow value of the photopolymerization initiator is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
ラジカル重合型樹脂組成物における光重合開始剤の含有量は、硬化性成分(ラジカル重合性化合物)の全量100重量部に対して、20重量部以下である。光重合開始剤の配合量は、0.01~20重量部であることが好ましく、0.05~10重量部であることがより好ましく、0.1~5重量部であることがさらに好ましい。
The content of the photopolymerization initiator in the radical polymerization type resin composition is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
ラジカル重合型樹脂組成物が可視光線硬化性化合物を含む場合、特に380nm以上の光に対して高感度な光重合開始剤を用いることが好ましい。
When the radical polymerization type resin composition contains a visible light curable compound, it is particularly preferable to use a photopolymerization initiator having high sensitivity to light of 380 nm or more.
光重合開始剤としては、下記一般式(4)で表される化合物(以下、「化合物(4)」ということがある。)が挙げられる。
Examples of the photopolymerization initiator include a compound represented by the following general formula (4) (hereinafter, may be referred to as “compound (4)”).
[式中、R11及びR12は、それぞれ独立して、-H、-CH2CH3、-iPr(イソプロピル基)又は-Clであり、R11及びR12は、互いに同じであってもよく異なっていてもよい。]
[In the formula, R 11 and R 12 are independently -H, -CH 2 CH 3 , -iPr (isopropyl group) or -Cl, and R 11 and R 12 may be the same as each other. It may be very different. ]
ラジカル重合型樹脂組成物において、化合物(4)は、単独で用いてもよく、後述する380nm以上の光に対して高感度な光重合開始剤と併用して用いてもよい。化合物(4)を用いることにより、380nm以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて、輝度向上フィルムと硬化物層との接着性を向上することができる。化合物(4)の中でも、R11及びR12が-CH2CH3であるジエチルチオキサントンが特に好ましい。ラジカル重合型樹脂組成物中の化合物(4)の含有量は、硬化性成分(ラジカル重合性化合物)の全量100重量部に対して、0.1~5重量部であることが好ましく、0.5~4重量部であることがより好ましく、0.9~3重量部であることがさらに好ましい。
In the radical polymerization type resin composition, the compound (4) may be used alone or in combination with a photopolymerization initiator having high sensitivity to light of 380 nm or more, which will be described later. By using the compound (4), the adhesiveness between the brightness improving film and the cured product layer can be improved as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. .. Among the compounds (4), diethylthioxanthone in which R 11 and R 12 are −CH 2 CH 3 is particularly preferable. The content of the compound (4) in the radical polymerization type resin composition is preferably 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component (radical polymerizable compound). It is more preferably 5 to 4 parts by weight, and even more preferably 0.9 to 3 parts by weight.
380nm以上の光に対して高感度な光重合開始剤としては、例えば、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等が挙げられる。
Examples of the photopolymerization initiator having high sensitivity to light of 380 nm or more include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino. -1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone , 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium and the like can be mentioned.
ラジカル重合型樹脂組成物は、化合物(4)に加えて、下記一般式(5)で表される化合物(以下、「化合物(5)」ということがある。)を含むことが好ましい。
The radical polymerization type resin composition preferably contains a compound represented by the following general formula (5) (hereinafter, may be referred to as "compound (5)") in addition to the compound (4).
[式中、R13、R14及びR15は、それぞれ独立して、-H、-CH3、-CH2CH3、-iPr又は-Clであり、R13、R14及びR15は、互いに同じであってもよく異なっていてもよい。]
[In the formula, R 13 , R 14 and R 15 are independently -H, -CH 3 , -CH 2 CH 3 , -iPr or -Cl, and R 13 , R 14 and R 15 are They may be the same or different from each other. ]
化合物(5)としては、例えば、市販品でもある2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(商品名:IRGACURE907、BASF社製)が好適に使用可能である。その他、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(商品名:IRGACURE369、BASF社製)、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン(商品名:IRGACURE379、BASF社製)も感度が高いため好ましい。
As the compound (5), for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE907, manufactured by BASF), which is also a commercially available product, can be preferably used. Is. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) is also preferable because of its high sensitivity.
ラジカル重合型樹脂組成物は、必要に応じて重合開始助剤を含んでいてもよい。重合開始助剤としては、トリエチルアミン、ジエチルアミン、N-メチルジエタノールアミン、エタノールアミン、4-ジメチルアミノ安息香酸、4-ジメチルアミノ安息香酸メチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル等が挙げられ、4-ジメチルアミノ安息香酸エチルが特に好ましい。重合開始助剤を使用する場合、ラジカル重合型樹脂組成物中の重合開始助剤の含有量は、硬化性成分(ラジカル重合性化合物)の全量100重量部に対して、通常0~5重量部、好ましくは0~4重量部、最も好ましくは0~3重量部である。
The radical polymerization type resin composition may contain a polymerization initiation aid, if necessary. Examples of the polymerization initiator include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and the like. , And ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiator is used, the content of the polymerization initiator in the radical polymerization type resin composition is usually 0 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). , Preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight.
(活性メチレン基を有するラジカル重合性化合物(a1)と、水素引き抜き作用のあるラジカル重合開始剤(a2))
ラジカル重合型樹脂組成物に含まれるラジカル重合性化合物として、活性メチレン基を有するラジカル重合性化合物(a1)を用いる場合には、水素引き抜き作用のあるラジカル重合開始剤(a2)と組み合わせて用いることが好ましい。このようなラジカル重合型樹脂組成物によれば、特に高湿度環境において、輝度向上フィルムに直接接するように硬化層を設けた場合にも良好な接着性を確保することができる。この理由は明らかではないが、次のように推測される。活性メチレン基を有するラジカル重合性化合物(a1)は、硬化物層を構成する他のラジカル重合性化合物とともに重合しつつ、硬化物層中のベースポリマーの主鎖及び/又は側鎖に取り込まれ、硬化物層を形成する。この重合過程において、水素引き抜き作用のあるラジカル重合開始剤(a2)が存在すると、硬化物層を構成するベースポリマーが形成されつつ、活性メチレン基を有するラジカル重合性化合物(a2)から水素が引き抜かれ、メチレン基にラジカルが発生する。そして、ラジカルが発生したメチレン基と輝度向上フィルムの水酸基とが反応し、硬化物層と輝度向上フィルムとの間に共有結合が形成される。その結果、特に高湿度環境であっても、輝度向上フィルムと硬化物層との接着性が向上すると考えられる。 (Radical polymerizable compound (a1) having an active methylene group and radical polymerization initiator (a2) having a hydrogen abstraction action)
When a radically polymerizable compound (a1) having an active methylene group is used as the radically polymerizable compound contained in the radically polymerizable resin composition, it should be used in combination with a radical polymerization initiator (a2) having a hydrogen abstraction action. Is preferable. According to such a radical polymerization type resin composition, good adhesiveness can be ensured even when a cured layer is provided so as to be in direct contact with the brightness improving film, particularly in a high humidity environment. The reason for this is not clear, but it is speculated as follows. The radically polymerizable compound (a1) having an active methylene group is incorporated into the main chain and / or side chain of the base polymer in the cured product layer while being polymerized together with other radically polymerizable compounds constituting the cured product layer. Form a cured product layer. In this polymerization process, when a radical polymerization initiator (a2) having a hydrogen abstraction action is present, hydrogen is drawn from the radical polymerizable compound (a2) having an active methylene group while forming the base polymer constituting the cured product layer. It is extracted and a radical is generated in the methylene group. Then, the methylene group in which radicals are generated reacts with the hydroxyl group of the brightness improving film, and a covalent bond is formed between the cured product layer and the brightness improving film. As a result, it is considered that the adhesiveness between the brightness improving film and the cured product layer is improved even in a particularly high humidity environment.
ラジカル重合型樹脂組成物に含まれるラジカル重合性化合物として、活性メチレン基を有するラジカル重合性化合物(a1)を用いる場合には、水素引き抜き作用のあるラジカル重合開始剤(a2)と組み合わせて用いることが好ましい。このようなラジカル重合型樹脂組成物によれば、特に高湿度環境において、輝度向上フィルムに直接接するように硬化層を設けた場合にも良好な接着性を確保することができる。この理由は明らかではないが、次のように推測される。活性メチレン基を有するラジカル重合性化合物(a1)は、硬化物層を構成する他のラジカル重合性化合物とともに重合しつつ、硬化物層中のベースポリマーの主鎖及び/又は側鎖に取り込まれ、硬化物層を形成する。この重合過程において、水素引き抜き作用のあるラジカル重合開始剤(a2)が存在すると、硬化物層を構成するベースポリマーが形成されつつ、活性メチレン基を有するラジカル重合性化合物(a2)から水素が引き抜かれ、メチレン基にラジカルが発生する。そして、ラジカルが発生したメチレン基と輝度向上フィルムの水酸基とが反応し、硬化物層と輝度向上フィルムとの間に共有結合が形成される。その結果、特に高湿度環境であっても、輝度向上フィルムと硬化物層との接着性が向上すると考えられる。 (Radical polymerizable compound (a1) having an active methylene group and radical polymerization initiator (a2) having a hydrogen abstraction action)
When a radically polymerizable compound (a1) having an active methylene group is used as the radically polymerizable compound contained in the radically polymerizable resin composition, it should be used in combination with a radical polymerization initiator (a2) having a hydrogen abstraction action. Is preferable. According to such a radical polymerization type resin composition, good adhesiveness can be ensured even when a cured layer is provided so as to be in direct contact with the brightness improving film, particularly in a high humidity environment. The reason for this is not clear, but it is speculated as follows. The radically polymerizable compound (a1) having an active methylene group is incorporated into the main chain and / or side chain of the base polymer in the cured product layer while being polymerized together with other radically polymerizable compounds constituting the cured product layer. Form a cured product layer. In this polymerization process, when a radical polymerization initiator (a2) having a hydrogen abstraction action is present, hydrogen is drawn from the radical polymerizable compound (a2) having an active methylene group while forming the base polymer constituting the cured product layer. It is extracted and a radical is generated in the methylene group. Then, the methylene group in which radicals are generated reacts with the hydroxyl group of the brightness improving film, and a covalent bond is formed between the cured product layer and the brightness improving film. As a result, it is considered that the adhesiveness between the brightness improving film and the cured product layer is improved even in a particularly high humidity environment.
水素引き抜き作用のあるラジカル重合開始剤(a2)として、例えばチオキサントン系ラジカル重合開始剤、ベンゾフェノン系ラジカル重合開始剤等が挙げられる。ラジカル重合開始剤(a2)は、チオキサントン系ラジカル重合開始剤であることが好ましい。チオキサントン系ラジカル重合開始剤としては、例えば、上記した化合物(4)が挙げられる。化合物(4)の具体例としては、例えば、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン等が挙げられる。化合物(4)の中でも、R11及びR12が-CH2CH3であるジエチルチオキサントンが特に好ましい。
Examples of the radical polymerization initiator (a2) having a hydrogen abstraction action include a thioxanthone-based radical polymerization initiator and a benzophenone-based radical polymerization initiator. The radical polymerization initiator (a2) is preferably a thioxanthone-based radical polymerization initiator. Examples of the thioxanthone-based radical polymerization initiator include the above-mentioned compound (4). Specific examples of compound (4) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and the like. Among the compounds (4), diethylthioxanthone in which R 11 and R 12 are −CH 2 CH 3 is particularly preferable.
ラジカル重合型樹脂組成物において、活性メチレン基を有するラジカル重合性化合物(a1)と、水素引き抜き作用のあるラジカル重合開始剤(a2)とを含有する場合には、硬化性成分(ラジカル重合性化合物)の全量を100重量%としたとき、活性メチレン基を有するラジカル重合性化合物(a1)を1~50重量%、及びラジカル重合開始剤(a2)を、硬化性成分の全量100重量部に対して0.1~10重量部含有することが好ましい。
When the radical polymerization type resin composition contains a radical polymerization compound (a1) having an active methylene group and a radical polymerization initiator (a2) having a hydrogen abstraction action, a curable component (radical polymerizable compound) is contained. ) Is 100% by weight, the radical polymerization compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is added to 100 parts by weight of the total amount of the curable component. It is preferably contained in an amount of 0.1 to 10 parts by weight.
上記したように、水素引き抜き作用のあるラジカル重合開始剤(a2)の存在下で、活性メチレン基を有するラジカル重合性化合物(a1)のメチレン基にラジカルを発生させ、かかるメチレン基と輝度向上フィルムの水酸基とが反応し、共有結合を形成すると考えられる。したがって、活性メチレン基を有するラジカル重合性化合物(a1)のメチレン基にラジカルを発生させ、かかる共有結合を十分に形成するために、硬化性成分(ラジカル重合性化合物)の全量を100重量%としたとき、活性メチレン基を有するラジカル重合性化合物(a1)を1~50重量%含有することが好ましく、さらには3~30重量%含有することがより好ましい。耐水性を十分に向上させて高湿度環境での輝度向上フィルムと硬化物層との接着性を向上させるためには活性メチレン基を有するラジカル重合性化合物(a1)は1重量%以上とすることが好ましい。一方、50重量%を超えると、硬化物層の硬化不良が発生する場合がある。また、水素引き抜き作用のあるラジカル重合開始剤(a2)は、硬化性成分の全量100重量部に対して0.1~10重量部含有することが好ましく、さらには0.3~9重量部含有することがより好ましい。水素引き抜き反応を十分に進行させるためには、ラジカル重合開始剤(a2)を0.1重量部以上用いることが好ましい。一方、10重量部を超えると、ラジカル重合型樹脂組成物中で完全に溶解しない場合がある。
As described above, in the presence of the radical polymerization initiator (a2) having a hydrogen abstraction action, radicals are generated in the methylene group of the radical polymerizable compound (a1) having an active methylene group, and the methylene group and the brightness improving film are formed. It is considered that the hydroxyl group reacts with the hydroxyl group to form a covalent bond. Therefore, in order to generate a radical in the methylene group of the radically polymerizable compound (a1) having an active methylene group and sufficiently form such a covalent bond, the total amount of the curable component (radical polymerizable compound) is set to 100% by weight. The radical polymerizable compound (a1) having an active methylene group is preferably contained in an amount of 1 to 50% by weight, more preferably 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesiveness between the brightness improving film and the cured product layer in a high humidity environment, the amount of the radically polymerizable compound (a1) having an active methylene group should be 1% by weight or more. Is preferable. On the other hand, if it exceeds 50% by weight, curing failure of the cured product layer may occur. Further, the radical polymerization initiator (a2) having a hydrogen abstraction action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. It is more preferable to do so. In order to sufficiently proceed with the hydrogen abstraction reaction, it is preferable to use 0.1 part by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not be completely dissolved in the radical polymerization type resin composition.
〔A2〕カチオン重合型樹脂組成物
カチオン重合型樹脂組成物は、硬化性成分としてカチオン重合性化合物を含む。カチオン重合性化合物は、分子内にカチオン重合性官能基を1つ有する単官能カチオン重合性化合物と、分子内にカチオン重合性官能基を2つ以上有する多官能カチオン重合性化合物とに分類される。単官能カチオン重合性化合物は比較的液粘度が低いため、カチオン重合型樹脂組成物に含有させることで該樹脂組成物の液粘度を低下させることができる。また、単官能カチオン重合性化合物は各種機能を発現させる官能基を有している場合が多く、カチオン重合型樹脂組成物に含有させることで該樹脂組成物及び/又は該樹脂組成物の硬化物層に各種機能を発現させることができる。 [A2] Cationic Polymerized Resin Composition The cationically polymerized resin composition contains a cationically polymerizable compound as a curable component. The cationically polymerizable compound is classified into a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. .. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be lowered by containing it in the cationically polymerizable resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that express various functions, and by containing them in a cationically polymerizable resin composition, the resin composition and / or a cured product of the resin composition Various functions can be expressed in the layer.
カチオン重合型樹脂組成物は、硬化性成分としてカチオン重合性化合物を含む。カチオン重合性化合物は、分子内にカチオン重合性官能基を1つ有する単官能カチオン重合性化合物と、分子内にカチオン重合性官能基を2つ以上有する多官能カチオン重合性化合物とに分類される。単官能カチオン重合性化合物は比較的液粘度が低いため、カチオン重合型樹脂組成物に含有させることで該樹脂組成物の液粘度を低下させることができる。また、単官能カチオン重合性化合物は各種機能を発現させる官能基を有している場合が多く、カチオン重合型樹脂組成物に含有させることで該樹脂組成物及び/又は該樹脂組成物の硬化物層に各種機能を発現させることができる。 [A2] Cationic Polymerized Resin Composition The cationically polymerized resin composition contains a cationically polymerizable compound as a curable component. The cationically polymerizable compound is classified into a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. .. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be lowered by containing it in the cationically polymerizable resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that express various functions, and by containing them in a cationically polymerizable resin composition, the resin composition and / or a cured product of the resin composition Various functions can be expressed in the layer.
多官能カチオン重合性化合物は、硬化物層を3次元架橋させることができるため、樹脂組成物に含有させることが好ましい。カチオン重合型樹脂組成物における単官能カチオン重合性化合物と多官能カチオン重合性化合物の配合比は、単官能カチオン重合性化合物100重量部に対して、多官能カチオン重合性化合物を10重量部以上1000重量部以下の範囲で含有することが好ましい。
The polyfunctional cationically polymerizable compound is preferably contained in the resin composition because the cured product layer can be three-dimensionally crosslinked. The blending ratio of the monofunctional cationically polymerizable compound and the polyfunctional cationically polymerizable compound in the cationically polymerizable resin composition is 10 parts by weight or more and 1000 parts by weight or more with respect to 100 parts by weight of the monofunctional cationically polymerizable compound. It is preferably contained in the range of parts by weight or less.
カチオン重合性官能基としては、エポキシ基やオキセタニル基、ビニルエーテル基が挙げられる。エポキシ基を有する化合物としては、脂肪族エポキシ化合物、脂環式エポキシ化合物、芳香族エポキシ化合物が挙げられ、カチオン重合型樹脂組成物としては、硬化性や接着性に優れることから、脂環式エポキシ化合物を含有することが特に好ましい。
Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound. As a cationically polymerizable resin composition, the alicyclic epoxy is excellent in curability and adhesiveness. It is particularly preferable to contain a compound.
脂環式エポキシ化合物としては、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレートのカプロラクトン変性物やトリメチルカプロラクトン変性物やバレロラクトン変性物等が挙げられ、具体的には、セロキサイド2021、セロキサイド2021A、セロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド2085(以上、ダイセル化学工業(株)製、サイラキュアUVR-6105、サイラキュアUVR-6107、サイラキュア30、R-6110(以上、ダウ・ケミカル日本(株)製)等が挙げられる。
Examples of the alicyclic epoxy compound include caprolactone-modified products and trimethylcaprolactone-modified products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. , Valerolactone modified products, etc., and specifically, seroxide 2021, seroxide 2021A, seroxide 2021P, seroxide 2081, seroxide 2083, seroxide 2085 (all manufactured by Daicel Chemical Industry Co., Ltd., Cyclocure UVR-6105, CyclohexylUVR). -6107, Cyracure 30, R-6110 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like can be mentioned.
オキセタニル基を有する化合物は、カチオン重合型樹脂組成物の硬化性を改善したり、該組成物の液粘度を低下させる効果があるため、含有させることが好ましい。オキセタニル基を有する化合物としては、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス[(3-エチル-3-オキセタニル)メトキシメチル]ベンゼン、3-エチル-3-(フェノキシメチル)オキセタン、ジ[(3-エチル-3-オキセタニル)メチル]エーテル、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン、フェノールノボラックオキセタン等が挙げられ、アロンオキセタンOXT-101、アロンオキセタンOXT-121、アロンオキセタンOXT-211、アロンオキセタンOXT-221、アロンオキセタンOXT-212(以上、東亞合成社製)等が市販されている。
A compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the cationically polymerized resin composition and lowering the liquid viscosity of the composition. Compounds having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, and the like. Di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane and the like can be mentioned, including Aron Oxetane OXT-101 and Aron Oxetane OXT-121. , Aron Oxetane OXT-221, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (all manufactured by Toa Synthetic Co., Ltd.) and the like are commercially available.
ビニルエーテル基を有する化合物は、カチオン重合型樹脂組成物の硬化性を改善したり、該組成物の液粘度を低下させる効果があるため、含有させることが好ましい。ビニルエーテル基を有する化合物としては、2-ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、4-ヒドロキシブチルビニルエーテル、ジエチレングリコールものビニルエーテル、トリエチレングリコールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、トリシクロデカンビニルエーテル、シクロヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、ペンタエリスリトール型テトラビニルエーテル等が挙げられる。
A compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationically polymerized resin composition and lowering the liquid viscosity of the composition. Examples of compounds having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, and tricyclodecane vinyl ether. , Cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol type tetravinyl ether and the like.
(光カチオン重合開始剤)
カチオン重合型樹脂組成物は、上記した硬化性成分であるエポキシ基を有する化合物、オキセタニル基を有する化合物、ビニルエーテル基を有する化合物から選ばれる少なくとも1つの化合物を含有する。これらの化合物は、いずれもカチオン重合により硬化するものであることから、カチオン重合型樹脂組成物は、さらに光カチオン重合開始剤を含むことが好ましい。この光カチオン重合開始剤は、可視光線、紫外線、X線、電子線等の活性エネルギー線の照射によって、カチオン種又はルイス酸を発生し、エポキシ基やオキセタニル基の重合反応を開始する。光カチオン重合開始剤としては、後述の光酸発生剤が好適に使用される。 (Photocationic polymerization initiator)
The cationically polymerizable resin composition contains at least one compound selected from the above-mentioned curable component having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group. Since all of these compounds are cured by cationic polymerization, it is preferable that the cationically polymerizable resin composition further contains a photocationic polymerization initiator. This photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group. As the photocationic polymerization initiator, a photoacid generator described later is preferably used.
カチオン重合型樹脂組成物は、上記した硬化性成分であるエポキシ基を有する化合物、オキセタニル基を有する化合物、ビニルエーテル基を有する化合物から選ばれる少なくとも1つの化合物を含有する。これらの化合物は、いずれもカチオン重合により硬化するものであることから、カチオン重合型樹脂組成物は、さらに光カチオン重合開始剤を含むことが好ましい。この光カチオン重合開始剤は、可視光線、紫外線、X線、電子線等の活性エネルギー線の照射によって、カチオン種又はルイス酸を発生し、エポキシ基やオキセタニル基の重合反応を開始する。光カチオン重合開始剤としては、後述の光酸発生剤が好適に使用される。 (Photocationic polymerization initiator)
The cationically polymerizable resin composition contains at least one compound selected from the above-mentioned curable component having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group. Since all of these compounds are cured by cationic polymerization, it is preferable that the cationically polymerizable resin composition further contains a photocationic polymerization initiator. This photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group. As the photocationic polymerization initiator, a photoacid generator described later is preferably used.
硬化性化合物を含む樹脂組成物が可視光線硬化性化合物を含む場合には、特に380nm以上の光に対して高感度な光カチオン重合開始剤を用いることが好ましいが、光カチオン重合開始剤は一般に、300nm付近またはそれより短い波長域に極大吸収を示す化合物であるため、それより長い波長域、具体的には380nmより長い波長の光に極大吸収を示す光増感剤を配合することで、この付近の波長の光に感応し、光カチオン重合開始剤からのカチオン種又は酸の発生を促進させることができる。光増感剤としては、例えば、アントラセン化合物、ピレン化合物、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ及びジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられ、これらは、2種類以上を混合して使用してもよい。特にアントラセン化合物は、光増感効果に優れるため好ましく、具体的にはアントラキュアUVS-1331、アントラキュアUVS-1221(川崎化成社製)が挙げられる。光増感剤の含有量は、0.1重量%~5重量%であることが好ましく、0.5重量%~3重量%であることがより好ましい。
When the resin composition containing the curable compound contains a visible light curable compound, it is particularly preferable to use a photocationic polymerization initiator having high sensitivity to light of 380 nm or more, but the photocationic polymerization initiator is generally used. Since it is a compound that exhibits maximum absorption in the wavelength range around 300 nm or shorter, it is possible to add a light sensitizer that exhibits maximum absorption to light in a longer wavelength range, specifically, a wavelength longer than 380 nm. Sensitive to light of a wavelength near this range, it is possible to promote the generation of cation species or acids from the photocationic polymerization initiator. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducing dyes and the like. Two or more types may be mixed and used. In particular, the anthracene compound is preferable because it has an excellent photosensitizing effect, and specific examples thereof include anthracene UVS-1331 and anthracene UVS-1221 (manufactured by Kawasaki Kasei Chemicals, Inc.). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, more preferably 0.5% by weight to 3% by weight.
〔A3〕その他の成分
活性エネルギー線硬化性化合物を含む樹脂組成物は、(メタ)アクリル系オリゴマー、光酸発生剤、エポキシ基又はアルコキシ基を含む化合物、シランカップリング剤、ビニルエーテル基を有する化合物、これら以外の添加剤を含んでいてもよい。以下、これらの成分について説明する。 [A3] Other components The resin composition containing the active energy ray-curable compound is a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group. , Additives other than these may be contained. Hereinafter, these components will be described.
活性エネルギー線硬化性化合物を含む樹脂組成物は、(メタ)アクリル系オリゴマー、光酸発生剤、エポキシ基又はアルコキシ基を含む化合物、シランカップリング剤、ビニルエーテル基を有する化合物、これら以外の添加剤を含んでいてもよい。以下、これらの成分について説明する。 [A3] Other components The resin composition containing the active energy ray-curable compound is a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group. , Additives other than these may be contained. Hereinafter, these components will be described.
((メタ)アクリル系オリゴマー)
ラジカル重合型樹脂組成物又はカチオン重合型樹脂組成物は、ラジカル重合性化合物又はカチオン重合性化合物(硬化性成分)に加えて、(メタ)アクリルモノマーを重合してなる(メタ)アクリル系オリゴマーを含有することができる。上記樹脂組成物中に、(メタ)アクリル系オリゴマーを含有することにより、該樹脂組成物に、活性エネルギー線を照射して硬化させる際の硬化収縮を低減し、硬化物層と輝度向上フィルムとの界面応力を低減することができる。その結果、上記樹脂組成物の硬化物層と輝度向上フィルムとの接着性の低下を抑制することができる。硬化物層の硬化収縮を十分に抑制するためには、硬化性成分の全量100重量部に対して、(メタ)アクリル系オリゴマーを3重量部以上含有することが好ましく、5重量部以上含有することが好ましい。上記樹脂組成物中の(メタ)アクリル系オリゴマーの含有量が多すぎると、該樹脂組成物に活性エネルギー線を照射した際の反応速度の低下が激しく、硬化不良となる場合がある。反応速度の低下を十分に抑制するためには、硬化性成分の全量100重量部に対して、(メタ)アクリル系オリゴマーを、20重量部以下含有することが好ましく、15重量部以下含有することがより好ましい。 ((Meta) acrylic oligomer)
The radically polymerizable resin composition or the cationically polymerizable resin composition comprises a (meth) acrylic oligomer obtained by polymerizing a (meth) acrylic monomer in addition to a radically polymerizable compound or a cationically polymerizable compound (curable component). Can be contained. By containing a (meth) acrylic oligomer in the resin composition, the curing shrinkage when the resin composition is irradiated with active energy rays to be cured is reduced, and the cured product layer and the brightness improving film are formed. The interfacial stress can be reduced. As a result, it is possible to suppress a decrease in the adhesiveness between the cured product layer of the resin composition and the brightness improving film. In order to sufficiently suppress the curing shrinkage of the cured product layer, it is preferable to contain 3 parts by weight or more of the (meth) acrylic oligomer with respect to 100 parts by weight of the total amount of the curable component, and 5 parts by weight or more is contained. Is preferable. If the content of the (meth) acrylic oligomer in the resin composition is too large, the reaction rate when the resin composition is irradiated with active energy rays is drastically reduced, which may result in poor curing. In order to sufficiently suppress a decrease in the reaction rate, it is preferable to contain 20 parts by weight or less of the (meth) acrylic oligomer, and 15 parts by weight or less, based on 100 parts by weight of the total amount of the curable component. Is more preferable.
ラジカル重合型樹脂組成物又はカチオン重合型樹脂組成物は、ラジカル重合性化合物又はカチオン重合性化合物(硬化性成分)に加えて、(メタ)アクリルモノマーを重合してなる(メタ)アクリル系オリゴマーを含有することができる。上記樹脂組成物中に、(メタ)アクリル系オリゴマーを含有することにより、該樹脂組成物に、活性エネルギー線を照射して硬化させる際の硬化収縮を低減し、硬化物層と輝度向上フィルムとの界面応力を低減することができる。その結果、上記樹脂組成物の硬化物層と輝度向上フィルムとの接着性の低下を抑制することができる。硬化物層の硬化収縮を十分に抑制するためには、硬化性成分の全量100重量部に対して、(メタ)アクリル系オリゴマーを3重量部以上含有することが好ましく、5重量部以上含有することが好ましい。上記樹脂組成物中の(メタ)アクリル系オリゴマーの含有量が多すぎると、該樹脂組成物に活性エネルギー線を照射した際の反応速度の低下が激しく、硬化不良となる場合がある。反応速度の低下を十分に抑制するためには、硬化性成分の全量100重量部に対して、(メタ)アクリル系オリゴマーを、20重量部以下含有することが好ましく、15重量部以下含有することがより好ましい。 ((Meta) acrylic oligomer)
The radically polymerizable resin composition or the cationically polymerizable resin composition comprises a (meth) acrylic oligomer obtained by polymerizing a (meth) acrylic monomer in addition to a radically polymerizable compound or a cationically polymerizable compound (curable component). Can be contained. By containing a (meth) acrylic oligomer in the resin composition, the curing shrinkage when the resin composition is irradiated with active energy rays to be cured is reduced, and the cured product layer and the brightness improving film are formed. The interfacial stress can be reduced. As a result, it is possible to suppress a decrease in the adhesiveness between the cured product layer of the resin composition and the brightness improving film. In order to sufficiently suppress the curing shrinkage of the cured product layer, it is preferable to contain 3 parts by weight or more of the (meth) acrylic oligomer with respect to 100 parts by weight of the total amount of the curable component, and 5 parts by weight or more is contained. Is preferable. If the content of the (meth) acrylic oligomer in the resin composition is too large, the reaction rate when the resin composition is irradiated with active energy rays is drastically reduced, which may result in poor curing. In order to sufficiently suppress a decrease in the reaction rate, it is preferable to contain 20 parts by weight or less of the (meth) acrylic oligomer, and 15 parts by weight or less, based on 100 parts by weight of the total amount of the curable component. Is more preferable.
ラジカル重合型樹脂組成物又はカチオン重合型樹脂組成物は、塗工時の作業性や均一性を考慮した場合、低粘度であることが好ましいため、(メタ)アクリル系オリゴマーも低粘度であることが好ましい。低粘度であって、かつ硬化物層の硬化収縮を防止できる(メタ)アクリル系オリゴマーとしては、重量平均分子量(Mw)が15000以下のものが好ましく、10000以下のものがより好ましく、5000以下のものが特に好ましい。
一方、硬化物層の硬化収縮を十分に抑制するためには、(メタ)アクリル系オリゴマーの重量平均分子量(Mw)が500以上であることが好ましく、1000以上であることがより好ましく、1500以上であることが特に好ましい。 Since the radical polymerization type resin composition or the cationic polymerization type resin composition preferably has a low viscosity in consideration of workability and uniformity during coating, the (meth) acrylic oligomer also has a low viscosity. Is preferable. As the (meth) acrylic oligomer having a low viscosity and capable of preventing the curing shrinkage of the cured product layer, those having a weight average molecular weight (Mw) of 15,000 or less are preferable, those having a weight average molecular weight (Mw) of 15,000 or less are more preferable, and those having a weight average molecular weight (Mw) of 10,000 or less are more preferable. Those are particularly preferable.
On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer, the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and 1500 or more. Is particularly preferable.
一方、硬化物層の硬化収縮を十分に抑制するためには、(メタ)アクリル系オリゴマーの重量平均分子量(Mw)が500以上であることが好ましく、1000以上であることがより好ましく、1500以上であることが特に好ましい。 Since the radical polymerization type resin composition or the cationic polymerization type resin composition preferably has a low viscosity in consideration of workability and uniformity during coating, the (meth) acrylic oligomer also has a low viscosity. Is preferable. As the (meth) acrylic oligomer having a low viscosity and capable of preventing the curing shrinkage of the cured product layer, those having a weight average molecular weight (Mw) of 15,000 or less are preferable, those having a weight average molecular weight (Mw) of 15,000 or less are more preferable, and those having a weight average molecular weight (Mw) of 10,000 or less are more preferable. Those are particularly preferable.
On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer, the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and 1500 or more. Is particularly preferable.
(メタ)アクリル系オリゴマーを構成する(メタ)アクリルモノマーとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、2-メチル-2-ニトロプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、t-ペンチル(メタ)アクリレート、3-ペンチル(メタ)アクリレート、2,2-ジメチルブチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、セチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、4-メチル-2-プロピルペンチル(メタ)アクリレート、N-オクタデシル(メタ)アクリレート等の(メタ)アクリル酸(炭素数1~20)アルキルエステル類;シクロアルキル(メタ)アクリレート(例えば、シクロヘキシル(メタ)アクリレート、シクロペンチル(メタ)アクリレート等);アラルキル(メタ)アクリレート(例えば、ベンジル(メタ)アクリレート等);多環式(メタ)アクリレート(例えば、2-イソボルニル(メタ)アクリレート、2-ノルボルニルメチル(メタ)アクリレート、5-ノルボルネン-2-イル-メチル(メタ)アクリレート、3-メチル-2-ノルボルニルメチル(メタ)アクリレート等);ヒドロキシル基含有(メタ)アクリル酸エステル類(例えば、ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2,3-ジヒドロキシプロピルメチル-ブチル(メタ)メタクリレート等);アルコキシ基又はフェノキシ基含有(メタ)アクリル酸エステル類(2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-メトキシメトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、エチルカルビトール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等);エポキシ基含有(メタ)アクリル酸エステル類(例えば、グリシジル(メタ)アクリレート等);ハロゲン含有(メタ)アクリル酸エステル類(例えば、2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,2-トリフルオロエチルエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、ヘキサフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート、ヘプタデカフルオロデシル(メタ)アクリレート等);アルキルアミノアルキル(メタ)アクリレート(例えば、ジメチルアミノエチル(メタ)アクリレート等)等が挙げられる。これら(メタ)アクリレートは、単独で又は2種以上を併用して用いることができる。
Examples of the (meth) acrylic monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2-methyl-2. -Nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl ( Meta) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) ) Alkyl esters of (meth) acrylic acid (1 to 20 carbon atoms) such as acrylate, 4-methyl-2-propylpentyl (meth) acrylate, N-octadecyl (meth) acrylate; cycloalkyl (meth) acrylate (eg,) Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.); Aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, etc.); Polycyclic (meth) acrylate (eg, 2-isobornyl (meth) acrylate, 2- Norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.); hydroxyl group-containing (meth) acrylic acid esters (For example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.); alkoxy group- or phenoxy group-containing (meth) acrylic acid esters (2) -Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate Etc.); Epoxy group-containing (meth) acrylic acid esters (eg, glycidyl (meth) acrylate, etc.); Halogen-containing (meth) acrylic acid esters (eg, 2,2,2-trifluoroethyl (meth) acrylate, etc.) 2,2,2-Trifluoroethyl ethyl Ta) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.); alkylaminoalkyl (meth) acrylate (eg, dimethyl) Aminoethyl (meth) acrylate, etc.) and the like. These (meth) acrylates can be used alone or in combination of two or more.
(メタ)アクリル系オリゴマーの具体例としては、東亞合成社製「ARUFON」、綜研化学社製「アクトフロー」、BASFジャパン社製「JONCRYL」等が挙げられる。(メタ)アクリル系オリゴマーのなかでも、logPow値が高いものが好ましい。(メタ)アクリル系オリゴマーのlogPow値は、好ましくは2以上、より好ましくは3以上、最も好ましくは4以上である。
Specific examples of the (meth) acrylic oligomer include "ARUFON" manufactured by Toagosei Co., Ltd., "Actflow" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan Ltd. Among the (meth) acrylic oligomers, those having a high logPow value are preferable. The logPow value of the (meth) acrylic oligomer is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
(光酸発生剤)
活性エネルギー線硬化性化合物を含む樹脂組成物は、光酸発生剤を含有することができる。上記樹脂組成物に、光酸発生剤を含有する場合、光酸発生剤を含有しない場合に比べて、硬化物層の耐水性及び耐久性を飛躍的に向上することができる。光酸発生剤は、下記一般式(6)で表すことができる。 (Photoacid generator)
The resin composition containing the active energy ray-curable compound can contain a photoacid generator. When the resin composition contains a photoacid generator, the water resistance and durability of the cured product layer can be dramatically improved as compared with the case where the photoacid generator is not contained. The photoacid generator can be represented by the following general formula (6).
活性エネルギー線硬化性化合物を含む樹脂組成物は、光酸発生剤を含有することができる。上記樹脂組成物に、光酸発生剤を含有する場合、光酸発生剤を含有しない場合に比べて、硬化物層の耐水性及び耐久性を飛躍的に向上することができる。光酸発生剤は、下記一般式(6)で表すことができる。 (Photoacid generator)
The resin composition containing the active energy ray-curable compound can contain a photoacid generator. When the resin composition contains a photoacid generator, the water resistance and durability of the cured product layer can be dramatically improved as compared with the case where the photoacid generator is not contained. The photoacid generator can be represented by the following general formula (6).
[式中、L+は、任意のオニウムカチオンを表す。また、X-は、PF6 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、ClO4 -、ジチオカルバメートアニオン、SCN-よりからなる群より選択されるカウンターアニオンを表す。]
[In the formula, L + represents any onium cation. Further, X - is, PF 6 -, SbF 6 - , AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, dithiocarbamate anion, SCN - counter anion more selected from the group consisting of Represents. ]
X-は、PF6
-、SbF6
-、又はAsF6
-が好ましく、PF6
-、又はSbF6
-がより好ましい。
For X − , PF 6 − , SbF 6 − , or AsF 6 − is preferable, and PF 6 − or SbF 6 − is more preferable.
光酸発生剤を構成する好ましいオニウム塩としては、例えば、「サイラキュアーUVI-6992」、「サイラキュアーUVI-6974」(以上、ダウ・ケミカル日本株式会社製)、「アデカオプトマーSP150」、「アデカオプトマーSP152」、「アデカオプトマーSP170」、「アデカオプトマーSP172」(以上、株式会社ADEKA製)、「IRGACURE250」(チバスペシャルティーケミカルズ社製)、「CI-5102」、「CI-2855」(以上、日本曹達社製)、「サンエイドSI-60L」、「サンエイドSI-80L」、「サンエイドSI-100L」、「サンエイドSI-110L」、「サンエイドSI-180L」(以上、三新化学社製)、「CPI-100P」、「CPI-100A」(以上、サンアプロ株式会社製)、「WPI-069」、「WPI-113」、「WPI-116」、「WPI-041」、「WPI-044」、「WPI-054」、「WPI-055」、「WPAG-281」、「WPAG-567」、「WPAG-596」(以上、和光純薬社製)が挙げられる。
Preferred onium salts constituting the photoacid generator include, for example, "Cyracure UVI-6992", "Cyracure UVI-6974" (all manufactured by Dow Chemical Japan Co., Ltd.), "Adeka Putmer SP150", and "" ADEKA OPTMER SP152 ”,“ ADEKA OPTMER SP170 ”,“ ADEKA PTMER SP172 ”(above, manufactured by ADEKA Corporation),“ IRGACURE250 ”(manufactured by Ciba Specialty Chemicals),“ CI-5102 ”,“ CI-2855 (Above, manufactured by Nippon Soda Co., Ltd.), "Sun Aid SI-60L", "Sun Aid SI-80L", "Sun Aid SI-100L", "Sun Aid SI-110L", "Sun Aid SI-180L" (above, Sanshin Kagaku) (Made by), "CPI-100P", "CPI-100A" (above, manufactured by Sun Appro Co., Ltd.), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI" Examples thereof include "-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", and "WPAG-596" (all manufactured by Wako Junyaku Co., Ltd.).
光酸発生剤は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、10重量部以下であり、0.01~10重量部であることが好ましく、0.05~5重量部であることがより好ましく、0.1~3重量部であることが特に好ましい。
The photoacid generator is 10 parts by weight or less, and 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.
(エポキシ基又はアルコキシ基を含む化合物)
活性エネルギー線硬化性化合物を含む樹脂組成物は、光酸発生剤とともに、エポキシ基又はアルコキシ基を含む化合物を含むことができる。 (Compound containing epoxy group or alkoxy group)
The resin composition containing an active energy ray-curable compound can contain a compound containing an epoxy group or an alkoxy group together with a photoacid generator.
活性エネルギー線硬化性化合物を含む樹脂組成物は、光酸発生剤とともに、エポキシ基又はアルコキシ基を含む化合物を含むことができる。 (Compound containing epoxy group or alkoxy group)
The resin composition containing an active energy ray-curable compound can contain a compound containing an epoxy group or an alkoxy group together with a photoacid generator.
エポキシ基を含む化合物としては、分子内に1個以上のエポキシ基を有する化合物又は分子内に2個以上のエポキシ基を有する化合物を挙げることができ、高分子化合物(エポキシ樹脂)であってもよい。これらの化合物を用いる場合は、エポキシ基との反応性を有する官能基を分子内に二つ以上有する化合物を併用してもよい。エポキシ基との反応性を有する官能基とは、例えば、カルボキシル基、フェノール性水酸基、メルカプト基、1級又は2級の芳香族アミノ基等が挙げられる。これらの官能基は、3次元硬化性を考慮して、一分子中に2つ以上有することが特に好ましい。
Examples of the compound containing an epoxy group include a compound having one or more epoxy groups in the molecule or a compound having two or more epoxy groups in the molecule, even if it is a polymer compound (epoxy resin). Good. When these compounds are used, a compound having two or more functional groups having reactivity with an epoxy group in the molecule may be used in combination. Examples of the functional group having reactivity with the epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
分子内に1個以上のエポキシ基を有する化合物としては、例えば、エポキシ樹脂が挙げられ、ビスフェノールAとエピクロルヒドリンから誘導されるビスフェノールA型エポキシ樹脂、ビスフェノールFとエピクロルヒドリンから誘導されるビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、3官能型エポキシ樹脂や4官能型エポキシ樹脂等の多官能型エポキシ樹脂;グリシジルエステル型エポキシ樹脂;グリシジルアミン型エポキシ樹脂;ヒダントイン型エポキシ樹脂;イソシアヌレート型エポキシ樹脂;脂肪族鎖状エポキシ樹脂等があり、これらのエポキシ樹脂はハロゲン化されていてもよく、水素添加されていてもよい。
Examples of the compound having one or more epoxy groups in the molecule include an epoxy resin, a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, and a bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin. , Bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene Polyfunctional epoxy resin such as type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin; glycidyl ester type epoxy resin; glycidylamine type epoxy resin; hidden toin type epoxy resin; There are isocyanurate type epoxy resins; aliphatic chain epoxy resins and the like, and these epoxy resins may be halogenated or hydrogenated.
市販されているエポキシ樹脂製品としては特に限定されないが、例えば、ジャパンエポキシレジン株式会社製のJERコート828、1001、801N、806、807、152、604、630、871、YX8000、YX8034、YX4000、DIC株式会社製のエピクロン830、EXA835LV、HP4032D、HP820、株式会社ADEKA製のEP4100シリーズ、EP4000シリーズ、EPUシリーズ、ダイセル化学株式会社製のセロキサイドシリーズ(2021、2021P、2083、2085、3000等)、エポリードシリーズ、EHPEシリーズ、新日鐵化学社製のYDシリーズ、YDFシリーズ、YDCNシリーズ、YDBシリーズ、フェノキシ樹脂(ビスフェノール類とエピクロルヒドリンより合成されるポリヒドロキシポリエーテルで両末端にエポキシ基を有する;YPシリーズ等)、ナガセケムテックス社製のデナコールシリーズ、共栄社化学社製のエポライトシリーズ等が挙げられる。これらのエポキシ樹脂は、2種以上を併用してもよい。
The epoxy resin products on the market are not particularly limited, but for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, DIC manufactured by Japan Epoxy Resin Co., Ltd. Epicron 830, EXA835LV, HP4032D, HP820 manufactured by ADEKA Co., Ltd., EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Serokiside series manufactured by Daicel Chemical Co., Ltd. (2021, 2021P, 2083, 2085, 3000, etc.), Epoxide series, EHPE series, YD series, YDF series, YDCN series, YDB series manufactured by Nippon Steel Chemical Co., Ltd., phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, which has epoxy groups at both ends; YP series, etc.), Denacol series manufactured by Nagase ChemteX Corporation, Epoxy series manufactured by Kyoeisha Chemical Co., Ltd., etc. Two or more of these epoxy resins may be used in combination.
分子内にアルコキシ基を有する化合物としては、分子内に1個以上のアルコキシル基を有するものであれば特に制限なく、公知のものを使用できる。このような化合物としては、メラミン化合物、アミノ樹脂、シランカップリング剤等が挙げられる。
The compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. Examples of such compounds include melamine compounds, amino resins, silane coupling agents and the like.
エポキシ基又はアルコキシ基を含む化合物は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、通常、30重量部以下含まれ、20重量部以下含むことが好ましい。エポキシ基又はアルコキシ基を含む化合物の含有量が多すぎると、輝度向上フィルムに対する硬化物層の接着性が低下し、落下試験に対する耐衝撃性が悪化する場合がある。エポキシ基又はアルコキシ基を含む化合物は、耐水性の点から、上記樹脂組成物に含まれる硬化性成分の全量100重量部に対して、2重量部以上含むことが好ましく、5重量部以上含むことがより好ましい。
The compound containing an epoxy group or an alkoxy group is usually contained in an amount of 30 parts by weight or less and 20 parts by weight or less based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. Is preferable. If the content of the compound containing an epoxy group or an alkoxy group is too large, the adhesiveness of the cured product layer to the luminance improving film may be lowered, and the impact resistance to the drop test may be deteriorated. From the viewpoint of water resistance, the compound containing an epoxy group or an alkoxy group preferably contains 2 parts by weight or more, and 5 parts by weight or more, based on 100 parts by weight of the total amount of the curable component contained in the resin composition. Is more preferable.
(シランカップリング剤)
活性エネルギー線硬化性化合物を含む樹脂組成物は、シランカップリング剤を含むことができる。この場合、シランカップリング剤は、活性エネルギー線硬化性の化合物であることが好ましいが、活性エネルギー線硬化性の化合物でなくても、硬化物層に耐水性を付与することができる。 (Silane coupling agent)
The resin composition containing the active energy ray-curable compound can contain a silane coupling agent. In this case, the silane coupling agent is preferably an active energy ray-curable compound, but even if it is not an active energy ray-curable compound, water resistance can be imparted to the cured product layer.
活性エネルギー線硬化性化合物を含む樹脂組成物は、シランカップリング剤を含むことができる。この場合、シランカップリング剤は、活性エネルギー線硬化性の化合物であることが好ましいが、活性エネルギー線硬化性の化合物でなくても、硬化物層に耐水性を付与することができる。 (Silane coupling agent)
The resin composition containing the active energy ray-curable compound can contain a silane coupling agent. In this case, the silane coupling agent is preferably an active energy ray-curable compound, but even if it is not an active energy ray-curable compound, water resistance can be imparted to the cured product layer.
活性エネルギー線硬化性のシランカップリング剤としては、例えば、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン等が挙げられる。このうち、3-メタクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリメトキシシランが好ましい。
Examples of the active energy ray-curable silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltri. Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methoxyloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be mentioned. Of these, 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane are preferable.
活性エネルギー線硬化性ではないシランカップリング剤としては、アミノ基を有するシランカップリング剤が好ましい。アミノ基を有するシランカップリング剤としては、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリイソプロポキシシラン、γ-アミノプロピルメチルジメトキシシラン、γ-アミノプロピルメチルジエトキシシラン、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリエトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジエトキシシラン、γ-(2-アミノエチル)アミノプロピルトリイソプロポキシシラン、γ-(2-(2-アミノエチル)アミノエチル)アミノプロピルトリメトキシシラン、γ-(6-アミノヘキシル)アミノプロピルトリメトキシシラン、3-(N-エチルアミノ)-2-メチルプロピルトリメトキシシラン、γ-ウレイドプロピルトリメトキシシラン、γ-ウレイドプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、N-ベンジル-γ-アミノプロピルトリメトキシシラン、N-ビニルベンジル-γ-アミノプロピルトリエトキシシラン、N-シクロヘキシルアミノメチルトリエトキシシラン、N-シクロヘキシルアミノメチルジエトキシメチルシラン、N-フェニルアミノメチルトリメトキシシラン、(2-アミノエチル)アミノメチルトリメトキシシラン、N,N’-ビス[3-(トリメトキシシリル)プロピル]エチレンジアミン等のアミノ基含有シラン類;N-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミン等のケチミン型シラン類が挙げられる。
As the silane coupling agent that is not active energy ray curable, a silane coupling agent having an amino group is preferable. Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropyl. Methyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-( 2-Aminoethyl) Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ-( 6-Aminohexyl) Aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, Amino group-containing silanes such as N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1) , 3-Dimethylbutylidene) -3- (Triethoxysilyl) -1-propaneamine and other ketimine-type silanes.
上記以外の活性エネルギー線硬化性ではないシランカップリング剤としては、3-ウレイドプロピルトリエトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリエトキシシラン、イミダゾールシラン等が挙げられる。
Examples of the non-active energy ray-curable silane coupling agent other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis. (Triethoxysilylpropyl) Tetrasulfide, 3-isocyanatepropyltriethoxysilane, imidazolesilane and the like can be mentioned.
これらのうち、良好な接着性を確保するためには、γ-アミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリエトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジエトキシシラン、N-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミンが好ましい。アミノ基を有するシランカップリング剤は、1種のみを用いてもよく、2種以上を組合わせて用いてもよい。
Of these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-Aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-Propanamine is preferred. As the silane coupling agent having an amino group, only one type may be used, or two or more types may be used in combination.
シランカップリング剤は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、0.01~20重量部含むことが好ましく、0.05~15重量部含むことがより好ましく、0.1~10重量部含むことがさらに好ましい。シランカップリング剤の含有量が多すぎると、上記樹脂組成物の保存安定性が悪化し、またシランカップリング剤の含有量が少なすぎると、接着耐水性の効果が発揮されにくい。
The silane coupling agent preferably contains 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is more preferable to contain parts, and it is further preferable to contain 0.1 to 10 parts by weight. If the content of the silane coupling agent is too large, the storage stability of the resin composition deteriorates, and if the content of the silane coupling agent is too small, the effect of adhesive water resistance is not easily exhibited.
(ビニルエーテル基を有する化合物)
活性エネルギー線硬化性化合物を含む樹脂組成物は、ビニルエーテル基を有する化合物を含むことができる。ビニルエーテル基を有する化合物を含有することにより、輝度向上フィルムと硬化物層との接着耐水性を向上させることができる。これは、ビニルエーテル基が輝度向上フィルムと相互作用し、接着力が高まるためと推測される。輝度向上フィルムと硬化物層との接着耐水性をさらに高めるために、ビニルエーテル基を有する化合物として、ラジカル重合性化合物を用いることが好ましい。ビニルエーテル基を有する化合物は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、0.1~19重量部含有することが好ましい。 (Compound with vinyl ether group)
The resin composition containing the active energy ray-curable compound can contain a compound having a vinyl ether group. By containing a compound having a vinyl ether group, the adhesive water resistance between the brightness improving film and the cured product layer can be improved. It is presumed that this is because the vinyl ether group interacts with the brightness improving film to increase the adhesive force. In order to further enhance the adhesive water resistance between the brightness improving film and the cured product layer, it is preferable to use a radically polymerizable compound as the compound having a vinyl ether group. The compound having a vinyl ether group is preferably contained in an amount of 0.1 to 19 parts by weight based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound.
活性エネルギー線硬化性化合物を含む樹脂組成物は、ビニルエーテル基を有する化合物を含むことができる。ビニルエーテル基を有する化合物を含有することにより、輝度向上フィルムと硬化物層との接着耐水性を向上させることができる。これは、ビニルエーテル基が輝度向上フィルムと相互作用し、接着力が高まるためと推測される。輝度向上フィルムと硬化物層との接着耐水性をさらに高めるために、ビニルエーテル基を有する化合物として、ラジカル重合性化合物を用いることが好ましい。ビニルエーテル基を有する化合物は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、0.1~19重量部含有することが好ましい。 (Compound with vinyl ether group)
The resin composition containing the active energy ray-curable compound can contain a compound having a vinyl ether group. By containing a compound having a vinyl ether group, the adhesive water resistance between the brightness improving film and the cured product layer can be improved. It is presumed that this is because the vinyl ether group interacts with the brightness improving film to increase the adhesive force. In order to further enhance the adhesive water resistance between the brightness improving film and the cured product layer, it is preferable to use a radically polymerizable compound as the compound having a vinyl ether group. The compound having a vinyl ether group is preferably contained in an amount of 0.1 to 19 parts by weight based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound.
(添加剤)
活性エネルギー線硬化性化合物を含む樹脂組成物は、上記した(メタ)アクリル系オリゴマー、光酸発生剤、エポキシ基又はアルコキシ基を含む化合物、シランカップリング剤、及びビニルエーテル基を有する化合物以外に、本発明の目的及び効果を損なわない範囲において、各種の添加剤を含んでいてもよい。かかる添加剤としては、エポキシ樹脂、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン-ブタジエンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコーン系オリゴマー、ポリスルフィド系オリゴマー等のポリマーあるいはオリゴマー;フェノチアジン、2,6-ジ-t-ブチル-4-メチルフェノール等の重合禁止剤;重合開始助剤;レベリング剤;濡れ性改良剤;界面活性剤;可塑剤;紫外線吸収剤;無機充填剤;顔料;染料等を挙げることができる。上記した添加剤のなかでも、logPow値が高いものが好ましい。上記した添加剤のlogPow値は、好ましくは2以上、より好ましくは3以上、最も好ましくは4以上である。上記添加剤は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、通常0~10重量部含み、0~5重量部含むことが好ましく、0~3重量部含むことがより好ましい。 (Additive)
The resin composition containing the active energy ray-curable compound includes a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group, in addition to the above-mentioned compounds having a vinyl ether group. Various additives may be contained as long as the object and effect of the present invention are not impaired. Examples of such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based oligomers. Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surface activity Agents; plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like. Among the above-mentioned additives, those having a high logPow value are preferable. The logPow value of the above-mentioned additive is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. The additive usually contains 0 to 10 parts by weight and preferably 0 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is more preferable to include ~ 3 parts by weight.
活性エネルギー線硬化性化合物を含む樹脂組成物は、上記した(メタ)アクリル系オリゴマー、光酸発生剤、エポキシ基又はアルコキシ基を含む化合物、シランカップリング剤、及びビニルエーテル基を有する化合物以外に、本発明の目的及び効果を損なわない範囲において、各種の添加剤を含んでいてもよい。かかる添加剤としては、エポキシ樹脂、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン-ブタジエンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコーン系オリゴマー、ポリスルフィド系オリゴマー等のポリマーあるいはオリゴマー;フェノチアジン、2,6-ジ-t-ブチル-4-メチルフェノール等の重合禁止剤;重合開始助剤;レベリング剤;濡れ性改良剤;界面活性剤;可塑剤;紫外線吸収剤;無機充填剤;顔料;染料等を挙げることができる。上記した添加剤のなかでも、logPow値が高いものが好ましい。上記した添加剤のlogPow値は、好ましくは2以上、より好ましくは3以上、最も好ましくは4以上である。上記添加剤は、活性エネルギー線硬化性化合物を含む樹脂組成物に含まれる硬化性成分の全量100重量部に対して、通常0~10重量部含み、0~5重量部含むことが好ましく、0~3重量部含むことがより好ましい。 (Additive)
The resin composition containing the active energy ray-curable compound includes a (meth) acrylic oligomer, a photoacid generator, a compound containing an epoxy group or an alkoxy group, a silane coupling agent, and a compound having a vinyl ether group, in addition to the above-mentioned compounds having a vinyl ether group. Various additives may be contained as long as the object and effect of the present invention are not impaired. Examples of such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based oligomers. Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surface activity Agents; plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like. Among the above-mentioned additives, those having a high logPow value are preferable. The logPow value of the above-mentioned additive is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. The additive usually contains 0 to 10 parts by weight and preferably 0 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component contained in the resin composition containing the active energy ray-curable compound. It is more preferable to include ~ 3 parts by weight.
〔B〕熱硬化性化合物
熱硬化性化合物としては、輝度向上フィルムと硬化物層との接着性の観点から、熱硬化型接着剤、ホットメルト接着剤等を用いることができる。具体的な例としては、天然ゴム接着剤、α-オレフィン系接着剤、ウレタン樹脂系接着剤、エチレン-酢酸ビニル樹脂エマルション接着剤、エチレン-酢酸ビニル樹脂系ホットメルト接着剤、エポキシ樹脂系接着剤、塩化ビニル樹脂溶剤系接着剤、クロロプレンゴム系接着剤、シアノアクリレート系接着剤、シリコーン系接着剤、スチレン-ブタジエンゴム溶剤系接着剤、ニトリルゴム系接着剤、ニトロセルロース系接着剤、反応性ホットメルト接着剤、フェノール樹脂系接着剤、変性シリコーン系接着剤、ポリエステル系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリイミド系接着剤、ポリウレタン樹脂ホットメルト接着剤、ポリオレフィン樹脂ホットメルト接着剤、ポリ酢酸ビニル樹脂溶剤系接着剤、ポリスチレン樹脂溶剤系接着剤、ポリビニルアルコール系接着剤、ポリビニルピロリドン樹脂系接着剤、ポリビニルブチラール系接着剤、ポリベンズイミダゾール接着剤、ポリメタクリレート樹脂溶剤系接着剤、メラミン樹脂系接着剤、ユリア樹脂系接着剤、レゾルシノール系接着剤等が挙げられる。このような接着剤は、1種単独又は2種以上を混合して使用することができ、接着剤の種類に応じたベースポリマーが用いられる。 [B] Thermosetting Compound As the thermosetting compound, a thermosetting adhesive, a hot melt adhesive, or the like can be used from the viewpoint of adhesiveness between the brightness improving film and the cured product layer. Specific examples include natural rubber adhesives, α-olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resin adhesives. , Vinyl chloride resin solvent adhesive, chloroprene rubber adhesive, cyanoacrylate adhesive, silicone adhesive, styrene-butadiene rubber solvent adhesive, nitrile rubber adhesive, nitrocellulose adhesive, reactive hot Melt adhesive, phenol resin adhesive, modified silicone adhesive, polyester hot melt adhesive, polyamide resin hot melt adhesive, polyimide adhesive, polyurethane resin hot melt adhesive, polyolefin resin hot melt adhesive, poly Vinyl acetate resin solvent-based adhesive, polystyrene resin solvent-based adhesive, polyvinyl alcohol-based adhesive, polyvinylpyrrolidone resin-based adhesive, polyvinyl butyral-based adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent-based adhesive, melamine resin Examples thereof include based adhesives, urea resin based adhesives, resorcinol based adhesives and the like. Such an adhesive can be used alone or in combination of two or more, and a base polymer corresponding to the type of the adhesive is used.
熱硬化性化合物としては、輝度向上フィルムと硬化物層との接着性の観点から、熱硬化型接着剤、ホットメルト接着剤等を用いることができる。具体的な例としては、天然ゴム接着剤、α-オレフィン系接着剤、ウレタン樹脂系接着剤、エチレン-酢酸ビニル樹脂エマルション接着剤、エチレン-酢酸ビニル樹脂系ホットメルト接着剤、エポキシ樹脂系接着剤、塩化ビニル樹脂溶剤系接着剤、クロロプレンゴム系接着剤、シアノアクリレート系接着剤、シリコーン系接着剤、スチレン-ブタジエンゴム溶剤系接着剤、ニトリルゴム系接着剤、ニトロセルロース系接着剤、反応性ホットメルト接着剤、フェノール樹脂系接着剤、変性シリコーン系接着剤、ポリエステル系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリイミド系接着剤、ポリウレタン樹脂ホットメルト接着剤、ポリオレフィン樹脂ホットメルト接着剤、ポリ酢酸ビニル樹脂溶剤系接着剤、ポリスチレン樹脂溶剤系接着剤、ポリビニルアルコール系接着剤、ポリビニルピロリドン樹脂系接着剤、ポリビニルブチラール系接着剤、ポリベンズイミダゾール接着剤、ポリメタクリレート樹脂溶剤系接着剤、メラミン樹脂系接着剤、ユリア樹脂系接着剤、レゾルシノール系接着剤等が挙げられる。このような接着剤は、1種単独又は2種以上を混合して使用することができ、接着剤の種類に応じたベースポリマーが用いられる。 [B] Thermosetting Compound As the thermosetting compound, a thermosetting adhesive, a hot melt adhesive, or the like can be used from the viewpoint of adhesiveness between the brightness improving film and the cured product layer. Specific examples include natural rubber adhesives, α-olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, and epoxy resin adhesives. , Vinyl chloride resin solvent adhesive, chloroprene rubber adhesive, cyanoacrylate adhesive, silicone adhesive, styrene-butadiene rubber solvent adhesive, nitrile rubber adhesive, nitrocellulose adhesive, reactive hot Melt adhesive, phenol resin adhesive, modified silicone adhesive, polyester hot melt adhesive, polyamide resin hot melt adhesive, polyimide adhesive, polyurethane resin hot melt adhesive, polyolefin resin hot melt adhesive, poly Vinyl acetate resin solvent-based adhesive, polystyrene resin solvent-based adhesive, polyvinyl alcohol-based adhesive, polyvinylpyrrolidone resin-based adhesive, polyvinyl butyral-based adhesive, polybenzimidazole adhesive, polymethacrylate resin solvent-based adhesive, melamine resin Examples thereof include based adhesives, urea resin based adhesives, resorcinol based adhesives and the like. Such an adhesive can be used alone or in combination of two or more, and a base polymer corresponding to the type of the adhesive is used.
熱硬化型接着剤は、加熱により熱硬化して固化することにより接着力を発現する。熱硬化型接着剤としては、例えば、エポキシ系熱硬化型接着剤、ウレタン系熱硬化型接着剤、アクリル系熱硬化型接着剤等が挙げられる。熱硬化型接着剤の硬化温度は、例えば、100~200℃である。
The thermosetting adhesive develops adhesive strength by being thermoset and solidified by heating. Examples of the thermosetting adhesive include epoxy-based thermosetting adhesives, urethane-based thermosetting adhesives, acrylic-based thermosetting adhesives, and the like. The curing temperature of the thermosetting adhesive is, for example, 100 to 200 ° C.
ホットメルト接着剤は、加熱により溶融又は軟化して、輝度向上フィルムに熱融着し、その後の冷却によって、固化することにより、輝度向上フィルムに接着する。ホットメルト接着剤としては、例えば、ゴム系ホットメルト接着剤、ポリエステル系ホットメルト接着剤、ポリオレフィン系ホットメルト接着剤、エチレン-酢酸ビニル樹脂系ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリウレタン樹脂ホットメルト接着剤等が挙げられる。ホットメルト接着剤の軟化温度(環球法)は、例えば、100~200℃である。また、ホットメルト接着剤の溶融粘度は、180℃で、例えば、100~30000mPa・sである。
The hot melt adhesive is melted or softened by heating, heat-sealed to the brightness improving film, and then solidified by cooling to adhere to the brightness improving film. Examples of the hot melt adhesive include rubber hot melt adhesives, polyester hot melt adhesives, polyolefin hot melt adhesives, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, and polyurethane resins. Examples include hot melt adhesives. The softening temperature (ring ball method) of the hot melt adhesive is, for example, 100 to 200 ° C. The melt viscosity of the hot melt adhesive is 180 ° C., for example, 100 to 30,000 mPa · s.
〔直線偏光層〕
直線偏光層は、無偏光の光を入射させたとき、吸収軸に直交する振動面をもつ直線偏光を透過させる性質を有する。直線偏光層は、ポリビニルアルコール(以下、「PVA」と略すこともある。)系樹脂フィルムを含むものであることが好ましい。 [Linearly polarized light layer]
The linearly polarized light layer has a property of transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis when unpolarized light is incident. The linearly polarizing layer preferably contains a polyvinyl alcohol (hereinafter, may be abbreviated as “PVA”)-based resin film.
直線偏光層は、無偏光の光を入射させたとき、吸収軸に直交する振動面をもつ直線偏光を透過させる性質を有する。直線偏光層は、ポリビニルアルコール(以下、「PVA」と略すこともある。)系樹脂フィルムを含むものであることが好ましい。 [Linearly polarized light layer]
The linearly polarized light layer has a property of transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis when unpolarized light is incident. The linearly polarizing layer preferably contains a polyvinyl alcohol (hereinafter, may be abbreviated as “PVA”)-based resin film.
PVA系樹脂フィルムを含む直線偏光層としては、例えば、ポリビニルアルコール(以下、「PVA」と略すこともある。)系フィルム、部分ホルマール化PVA系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質による染色処理、及び延伸処理が施されたもの等が挙げられる。光学特性に優れることから、PVA系樹脂フィルムをヨウ素で染色し一軸延伸して得られた直線偏光層を用いることが好ましい。
Examples of the linearly polarizing layer containing the PVA-based resin film include a polyvinyl alcohol (hereinafter, may be abbreviated as "PVA") -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film. Examples thereof include those obtained by subjecting a hydrophilic polymer film such as, etc. to a dyeing treatment with a bicolor substance such as iodine or a bicolor dye, and a stretching treatment. Since it is excellent in optical characteristics, it is preferable to use a linearly polarizing layer obtained by dyeing a PVA-based resin film with iodine and uniaxially stretching it.
ポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をケン化することにより製造できる。ポリ酢酸ビニル系樹脂は、酢酸ビニルの単独重合体であるポリ酢酸ビニルのほか、酢酸ビニルと酢酸ビニルに共重合可能な他の単量体との共重合体であることもできる。酢酸ビニルに共重合可能な他の単量体としては、例えば、不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類、アンモニウム基を有するアクリルアミド類等が挙げられる。
The polyvinyl alcohol-based resin can be produced by saponifying the polyvinyl acetate-based resin. The polyvinyl acetate-based resin can be a copolymer of polyvinyl acetate, which is a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and another monomer copolymerizable with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
ポリビニルアルコール系樹脂のケン化度は、通常85~100モル%程度であり、好ましくは98モル%以上である。ポリビニルアルコール系樹脂は変性されていてもよく、例えば、アルデヒド類で変性されたポリビニルホルマールやポリビニルアセタール等も使用可能である。ポリビニルアルコール系樹脂の重合度は、通常1,000~10,000程度であり、好ましくは1,500~5,000程度である。
The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.
このようなポリビニルアルコール系樹脂を製膜したものが、直線偏光層の原反フィルムとして用いられる。ポリビニルアルコール系樹脂を製膜する方法は、特に限定されるものでなく、公知の方法で製膜することができる。ポリビニルアルコール系樹脂原反フィルムの膜厚は、例えば10~100μm程度、好ましくは10~60μm程度、より好ましくは15~30μm程度である。
A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a linearly polarizing layer. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based resin raw film is, for example, about 10 to 100 μm, preferably about 10 to 60 μm, and more preferably about 15 to 30 μm.
その他のPVA系樹脂フィルムを含む直線偏光層の製造方法としては、まず基材フィルムを用意し、基材フィルム上にポリビニルアルコール系樹脂等の樹脂の溶液を塗布し、溶媒を除去する乾燥等を行って基材フィルム上に樹脂層を形成する工程を含むものを挙げることができる。なお、基材フィルムの樹脂層が形成される面には、予めプライマー層を形成することができる。基材フィルムとしては、PET等の樹脂フィルムを使用できる。プライマー層の材料としては、直線偏光層に用いられる親水性樹脂を架橋した樹脂等を挙げることができる。
As another method for producing a linear polarizing layer containing a PVA-based resin film, first prepare a base film, apply a resin solution such as a polyvinyl alcohol-based resin on the base film, and dry the base film to remove the solvent. Examples thereof include a step of forming a resin layer on the base film. A primer layer can be formed in advance on the surface of the base film on which the resin layer is formed. As the base film, a resin film such as PET can be used. Examples of the material of the primer layer include a resin obtained by cross-linking a hydrophilic resin used for the linearly polarizing layer.
次いで、必要に応じて樹脂層の水分等の溶媒量を調整し、その後、基材フィルム及び樹脂層を一軸延伸し、続いて、樹脂層をヨウ素等の二色性色素で染色して二色性色素を樹脂層に吸着配向させる。続いて、必要に応じて二色性色素が吸着配向した樹脂層をホウ酸水溶液で処理し、ホウ酸水溶液を洗い落とす洗浄工程を行う。これにより、二色性色素が吸着配向された樹脂層、すなわち、直線偏光層のフィルムが製造される。各工程には公知の方法を採用できる。
Then, if necessary, the amount of solvent such as water content of the resin layer is adjusted, then the base film and the resin layer are uniaxially stretched, and then the resin layer is dyed with a bicolor dye such as iodine to obtain two colors. The sex dye is adsorbed and oriented on the resin layer. Subsequently, if necessary, the resin layer in which the dichroic dye is adsorbed and oriented is treated with a boric acid aqueous solution, and a washing step of washing off the boric acid aqueous solution is performed. As a result, a film of a resin layer in which the dichroic dye is adsorption-oriented, that is, a linearly polarizing layer is produced. A known method can be adopted for each step.
基材フィルム及び樹脂層の一軸延伸は、染色の前に行ってもよいし、染色中に行ってもよいし、染色後のホウ酸処理中に行ってもよく、これら複数の段階においてそれぞれ一軸延伸を行ってもよい。基材フィルム及び樹脂層は、MD方向(フィルム搬送方向)に一軸延伸してもよく、この場合、周速の異なるロール間で一軸に延伸してもよいし、熱ロールを用いて一軸に延伸してもよい。また、基材フィルム及び樹脂層は、TD方向(フィルム搬送方向に垂直な方向)に一軸延伸してもよく、この場合、いわゆるテンター法を使用することができる。また、基材フィルム及び樹脂層の延伸は、大気中で延伸を行う乾式延伸であってもよいし、溶剤にて樹脂層を膨潤させた状態で延伸を行う湿式延伸であってもよい。直線偏光層の性能を発現するためには延伸倍率は4倍以上であり、5倍以上であることが好ましく、特に5.5倍以上が好ましい。延伸倍率の上限は特にないが、破断等を抑制する観点から8倍以下が好ましい。
The uniaxial stretching of the base film and the resin layer may be performed before dyeing, during dyeing, or during boric acid treatment after dyeing, and each of these multiple steps is uniaxial. Stretching may be performed. The base film and the resin layer may be uniaxially stretched in the MD direction (film transport direction), in this case, uniaxially stretched between rolls having different peripheral speeds, or uniaxially stretched using a thermal roll. You may. Further, the base film and the resin layer may be uniaxially stretched in the TD direction (direction perpendicular to the film transport direction), and in this case, the so-called tenter method can be used. Further, the stretching of the base film and the resin layer may be a dry stretching in which the resin layer is stretched in the air, or a wet stretching in which the resin layer is swollen with a solvent. In order to exhibit the performance of the linearly polarized light layer, the draw ratio is 4 times or more, preferably 5 times or more, and particularly preferably 5.5 times or more. There is no particular upper limit to the draw ratio, but it is preferably 8 times or less from the viewpoint of suppressing breakage and the like.
上記方法で作製した直線偏光層は、後述する保護層を積層した後に基材フィルムを剥離することで得ることができる。
The linearly polarized light layer produced by the above method can be obtained by laminating a protective layer described later and then peeling off the base film.
直線偏光層の厚みは、5μm以上であることが好ましく、10μm以上であることがより好ましく、15μm以上であってもよく、20μm以上であってもよい。また、直線偏光層の厚みは、50μm以下であり、40μm以下であることが好ましく、30μm以下であってもよい。
The thickness of the linearly polarizing layer is preferably 5 μm or more, more preferably 10 μm or more, 15 μm or more, or 20 μm or more. The thickness of the linearly polarizing layer is 50 μm or less, preferably 40 μm or less, and may be 30 μm or less.
〔偏光板〕
直線偏光層はその片面又は両面に、公知の粘着剤層又は接着層を介して、第1保護層、又は、第1保護層及び第2保護層(以下、第1保護層及び第2保護層をまとめて「保護層」ということがある。)を積層して偏光板とすることができる。この偏光板はいわゆる直線偏光板である。直線偏光層の片面又は両面に積層することができる保護層としては、例えば、透明性、機械的強度、熱安定性、水分遮断性、等方性、延伸性等に優れる熱可塑性樹脂から形成されたフィルムが用いられる。このような熱可塑性樹脂の具体例としては、トリアセチルセルロース等のセルロース樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂;ポリエーテルスルホン樹脂;ポリスルホン樹脂;ポリカーボネート樹脂;ナイロンや芳香族ポリアミド等のポリアミド樹脂;ポリイミド樹脂;ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体等のポリオレフィン樹脂;シクロ系及びノルボルネン構造を有する環状ポリオレフィン樹脂(ノルボルネン系樹脂ともいう);(メタ)アクリル樹脂;ポリアリレート樹脂;ポリスチレン樹脂;ポリビニルアルコール樹脂、並びにこれらの混合物を挙げることができる。直線偏光層の両面に保護層が積層されている場合、二つの保護層の樹脂組成は同一であってもよいし、異なっていてもよい。 〔Polarizer〕
The linearly polarizing layer has a first protective layer or a first protective layer and a second protective layer (hereinafter, first protective layer and second protective layer) via a known pressure-sensitive adhesive layer or adhesive layer on one or both sides thereof. Can be collectively referred to as a "protective layer") to form a polarizing plate. This polarizing plate is a so-called linear polarizing plate. The protective layer that can be laminated on one side or both sides of the linearly polarizing layer is formed of, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, stretchability, and the like. Film is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether sulfone resins; polysulfone resins; polycarbonate resins; polyamides such as nylon and aromatic polyamides. Resin; Polygon resin; Polyethylene resin such as polyethylene, polypropylene, ethylene / propylene copolymer; Cyclic polyolefin resin having cyclo-based and norbornene structure (also referred to as norbornene-based resin); (meth) acrylic resin; polyallylate resin; polystyrene resin Polyvinyl alcohol resins, as well as mixtures thereof, can be mentioned. When the protective layers are laminated on both sides of the linearly polarizing layer, the resin compositions of the two protective layers may be the same or different.
直線偏光層はその片面又は両面に、公知の粘着剤層又は接着層を介して、第1保護層、又は、第1保護層及び第2保護層(以下、第1保護層及び第2保護層をまとめて「保護層」ということがある。)を積層して偏光板とすることができる。この偏光板はいわゆる直線偏光板である。直線偏光層の片面又は両面に積層することができる保護層としては、例えば、透明性、機械的強度、熱安定性、水分遮断性、等方性、延伸性等に優れる熱可塑性樹脂から形成されたフィルムが用いられる。このような熱可塑性樹脂の具体例としては、トリアセチルセルロース等のセルロース樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂;ポリエーテルスルホン樹脂;ポリスルホン樹脂;ポリカーボネート樹脂;ナイロンや芳香族ポリアミド等のポリアミド樹脂;ポリイミド樹脂;ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体等のポリオレフィン樹脂;シクロ系及びノルボルネン構造を有する環状ポリオレフィン樹脂(ノルボルネン系樹脂ともいう);(メタ)アクリル樹脂;ポリアリレート樹脂;ポリスチレン樹脂;ポリビニルアルコール樹脂、並びにこれらの混合物を挙げることができる。直線偏光層の両面に保護層が積層されている場合、二つの保護層の樹脂組成は同一であってもよいし、異なっていてもよい。 〔Polarizer〕
The linearly polarizing layer has a first protective layer or a first protective layer and a second protective layer (hereinafter, first protective layer and second protective layer) via a known pressure-sensitive adhesive layer or adhesive layer on one or both sides thereof. Can be collectively referred to as a "protective layer") to form a polarizing plate. This polarizing plate is a so-called linear polarizing plate. The protective layer that can be laminated on one side or both sides of the linearly polarizing layer is formed of, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, stretchability, and the like. Film is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether sulfone resins; polysulfone resins; polycarbonate resins; polyamides such as nylon and aromatic polyamides. Resin; Polygon resin; Polyethylene resin such as polyethylene, polypropylene, ethylene / propylene copolymer; Cyclic polyolefin resin having cyclo-based and norbornene structure (also referred to as norbornene-based resin); (meth) acrylic resin; polyallylate resin; polystyrene resin Polyvinyl alcohol resins, as well as mixtures thereof, can be mentioned. When the protective layers are laminated on both sides of the linearly polarizing layer, the resin compositions of the two protective layers may be the same or different.
熱可塑性樹脂から形成されたフィルムは、直線偏光層との密着性を向上するため、表面処理(例えば、コロナ処理等)が施されていてもよく、プライマー層(下塗り層ともいう)等の薄層が形成されていてもよい。
The film formed from the thermoplastic resin may be surface-treated (for example, corona-treated) in order to improve the adhesion to the linearly polarizing layer, and the primer layer (also referred to as the undercoat layer) is thin. Layers may be formed.
保護層は、例えば上記の熱可塑性樹脂を延伸したものであってもよいし、延伸されていないものであってもよい(以下、「未延伸樹脂」ということがある。)。延伸処理としては、一軸延伸や二軸延伸等が挙げられる。
The protective layer may be, for example, one in which the above-mentioned thermoplastic resin is stretched or one in which the above-mentioned thermoplastic resin is not stretched (hereinafter, may be referred to as “unstretched resin”). Examples of the stretching treatment include uniaxial stretching and biaxial stretching.
直線偏光層に保護層を積層するために用いる粘着剤層としては、後述する第1粘着剤層等において説明する粘着剤が挙げられる。直線偏光層に保護層を積層するために用いる接着剤層としては、公知の接着剤を用いることができる。接着剤としては、感圧型接着剤(粘着剤)以外の接着剤であって、例えば、水系接着剤、活性エネルギー線硬化性接着剤が挙げられる。水系接着剤としては、例えば、ポリビニルアルコール系樹脂を水に溶解、又は分散させた接着剤が挙げられる。活性エネルギー線硬化性接着剤としては、例えば、紫外線、可視光、電子線、X線のような活性エネルギー線の照射によって硬化する硬化性化合物を含む無溶剤型の活性エネルギー線硬化性接着剤が挙げられる。
Examples of the pressure-sensitive adhesive layer used for laminating the protective layer on the linearly polarized light layer include the pressure-sensitive adhesive described in the first pressure-sensitive adhesive layer and the like described later. A known adhesive can be used as the adhesive layer used for laminating the protective layer on the linearly polarized light layer. Examples of the adhesive include adhesives other than pressure-sensitive adhesives (adhesives), such as water-based adhesives and active energy ray-curable adhesives. Examples of the water-based adhesive include an adhesive in which a polyvinyl alcohol-based resin is dissolved or dispersed in water. Examples of the active energy ray-curable adhesive include solvent-free active energy ray-curable adhesives containing a curable compound that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. Can be mentioned.
〔輝度向上フィルム〕
輝度向上フィルムは、バックライト等の光源からの出射光を透過偏光と反射偏光又は散乱偏光に分離するような機能を有する偏光変換素子が用いられる。輝度向上フィルムは、反射偏光又は散乱偏光の光源からの再帰光を利用して、直線偏光の出射効率を向上することができる。 [Brightness improvement film]
As the brightness improving film, a polarization conversion element having a function of separating the emitted light from a light source such as a backlight into transmitted polarized light and reflected polarized light or scattered polarized light is used. The brightness improving film can improve the emission efficiency of linearly polarized light by utilizing the retrolight from the light source of reflected polarized light or scattered polarized light.
輝度向上フィルムは、バックライト等の光源からの出射光を透過偏光と反射偏光又は散乱偏光に分離するような機能を有する偏光変換素子が用いられる。輝度向上フィルムは、反射偏光又は散乱偏光の光源からの再帰光を利用して、直線偏光の出射効率を向上することができる。 [Brightness improvement film]
As the brightness improving film, a polarization conversion element having a function of separating the emitted light from a light source such as a backlight into transmitted polarized light and reflected polarized light or scattered polarized light is used. The brightness improving film can improve the emission efficiency of linearly polarized light by utilizing the retrolight from the light source of reflected polarized light or scattered polarized light.
輝度向上フィルムとして、異方性反射偏光子を用いることができる。異方性反射偏光子は、例えば、誘電体の多層膜や屈折率異方性が互いに相違する層の多層積層体のように、所定偏光軸の直線偏光を透過して他の光は反射する特性を示すもの、コレステリック液晶ポリマーの配向フィルムやその配向液晶層をフィルム基材上に支持したもののように、左回り又は右回りのいずれか一方の円偏光を反射して他の光は透過する特性を示すもの等が挙げられる。異方性反射偏光子を構成する層の種類は、2種又はそれ以上とすることができる。
An anisotropic reflection polarizer can be used as the brightness improving film. Anisotropy reflectors transmit linearly polarized light of a predetermined polarization axis and reflect other light, such as a multilayer film of dielectrics and a multilayer laminate of layers having different refractive anisotropies. It reflects either left-handed or right-handed circularly polarized light and transmits other light, such as those exhibiting properties, an oriented film of cholesteric liquid crystal polymer or one in which the oriented liquid crystal layer is supported on a film substrate. Those showing characteristics and the like can be mentioned. The types of layers constituting the anisotropic reflection polarizer may be two or more.
輝度向上フィルムとしては、例えば、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリカーボネートに代表される延伸により位相差を発生する材料と、ポリメチルメタクリレートに代表されるアクリル系樹脂、JSR株式会社製の“アートン”(登録商標)に代表されるノルボルネン系樹脂等の位相差発現量の少ない樹脂とを交互に積層したものを一軸延伸して得られる積層体を用いることができる。このような構造体の具体例としては、3M社製の“DBEF”(登録商標)、“APF‐V4”(製品名)、“APF‐V3”(製品名)及び“APF‐V2”(製品名)等が挙げられる。
Examples of the brightness improving film include a material that generates a phase difference due to stretching represented by polyethylene naphthalate, polyethylene terephthalate, and polycarbonate, an acrylic resin represented by polymethylmethacrylate, and "Arton" manufactured by JSR Corporation. A laminate obtained by uniaxially stretching a resin obtained by alternately laminating a resin having a small amount of phase difference expression such as a norbornene-based resin typified by (registered trademark) can be used. Specific examples of such a structure include "DBEF" (registered trademark), "APF-V4" (product name), "APF-V3" (product name) and "APF-V2" (product name) manufactured by 3M. First name) and so on.
輝度向上フィルムは、例えば、コレステリック液晶層とλ/4板との積層体であってもよい。このような積層体の具体例としては、日東電工株式会社製の商品名“PCF”が挙げられる。
The brightness improving film may be, for example, a laminate of a cholesteric liquid crystal layer and a λ / 4 plate. Specific examples of such a laminate include the trade name "PCF" manufactured by Nitto Denko KK.
輝度向上フィルムは、反射グリッド偏光子であってもよい。反射グリッド偏光子としては、金属に微細加工を施し可視光領域でも反射偏光を出すような金属格子反射偏光子が挙げられる。
The brightness improving film may be a reflective grid polarizer. Examples of the reflection grid polarizer include a metal grid reflection polarizer in which the metal is finely processed to generate reflected polarized light even in the visible light region.
輝度向上フィルムの厚みは、通常5μm以上であり、10μm以上であってもよく、また、通常100μm以下であり、50μm以下であることが好ましく、35μm以下であってもよい。
The thickness of the luminance improving film is usually 5 μm or more and may be 10 μm or more, and is usually 100 μm or less, preferably 50 μm or less, and may be 35 μm or less.
〔第1粘着剤層、第2粘着剤層、第3粘着剤層〕
第1粘着剤層、第2粘着剤層、及び第3粘着剤層(以下、これらをまとめて「粘着剤層」ということがある。)は、粘着剤で構成された層である。本明細書において「粘着剤」とは、それ自体を偏光板や液晶層等の被着体に張り付けることで接着性を発現するものであり、いわゆる感圧型接着剤と称されるものである。また、後述する活性エネルギー線硬化型粘着剤は、エネルギー線を照射することにより、架橋度や接着力を調整することができる。 [First adhesive layer, second adhesive layer, third adhesive layer]
The first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer (hereinafter, these may be collectively referred to as "sticking agent layer") are layers composed of a pressure-sensitive adhesive. In the present specification, the "adhesive" exhibits adhesiveness by sticking itself to an adherend such as a polarizing plate or a liquid crystal layer, and is a so-called pressure-sensitive adhesive. .. Further, the active energy ray-curable pressure-sensitive adhesive described later can adjust the degree of cross-linking and the adhesive force by irradiating with energy rays.
第1粘着剤層、第2粘着剤層、及び第3粘着剤層(以下、これらをまとめて「粘着剤層」ということがある。)は、粘着剤で構成された層である。本明細書において「粘着剤」とは、それ自体を偏光板や液晶層等の被着体に張り付けることで接着性を発現するものであり、いわゆる感圧型接着剤と称されるものである。また、後述する活性エネルギー線硬化型粘着剤は、エネルギー線を照射することにより、架橋度や接着力を調整することができる。 [First adhesive layer, second adhesive layer, third adhesive layer]
The first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer (hereinafter, these may be collectively referred to as "sticking agent layer") are layers composed of a pressure-sensitive adhesive. In the present specification, the "adhesive" exhibits adhesiveness by sticking itself to an adherend such as a polarizing plate or a liquid crystal layer, and is a so-called pressure-sensitive adhesive. .. Further, the active energy ray-curable pressure-sensitive adhesive described later can adjust the degree of cross-linking and the adhesive force by irradiating with energy rays.
粘着剤としては、従来公知の光学的な透明性に優れる粘着剤を特に制限なく用いることができ、例えば、アクリル系、ウレタン系、シリコーン系、ポリビニルエーテル系等のベースポリマーを有する粘着剤を用いることができる。また、活性エネルギー線硬化型粘着剤、熱硬化型粘着剤等であってもよい。これらの中でも、透明性、粘着力、再剥離性(以下、リワーク性ともいう。)、耐候性、耐熱性等に優れるアクリル系樹脂をベースポリマーとした粘着剤が好適である。粘着剤層は、(メタ)アクリル系樹脂、架橋剤、シラン化合物を含む粘着剤組成物の反応生成物から構成されることが好ましく、その他の成分を含んでいてもよい。
As the pressure-sensitive adhesive, a conventionally known pressure-sensitive adhesive having excellent optical transparency can be used without particular limitation. For example, a pressure-sensitive adhesive having a base polymer such as an acrylic type, a urethane type, a silicone type, or a polyvinyl ether type is used. be able to. Further, it may be an active energy ray-curable pressure-sensitive adhesive, a thermosetting pressure-sensitive adhesive or the like. Among these, an adhesive based on an acrylic resin having excellent transparency, adhesive strength, removability (hereinafter, also referred to as reworkability), weather resistance, heat resistance and the like is preferable. The pressure-sensitive adhesive layer is preferably composed of a reaction product of a pressure-sensitive adhesive composition containing a (meth) acrylic resin, a cross-linking agent, and a silane compound, and may contain other components.
粘着剤層は、活性エネルギー線硬化型粘着剤を用いて形成してもよい。活性エネルギー線硬化型粘着剤は、粘着剤組成物に、多官能性アクリレート等の紫外線硬化性化合物を配合し、粘着剤層を形成した後に紫外線を照射して硬化させることにより、より硬い粘着剤層を形成することができる。活性エネルギー線硬化型粘着剤は、紫外線や電子線等のエネルギー線の照射を受けて硬化する性質を有している。活性化エネルギー線硬化型粘着剤は、エネルギー線照射前においても粘着性を有しているため、光学フィルムや液晶層等の被着体に密着し、エネルギー線の照射により硬化して密着力を調整することができる性質を有する粘着剤である。
The pressure-sensitive adhesive layer may be formed by using an active energy ray-curable pressure-sensitive adhesive. The active energy ray-curable pressure-sensitive adhesive is a harder pressure-sensitive adhesive by blending a pressure-sensitive adhesive composition with an ultraviolet-curable compound such as a polyfunctional acrylate, forming a pressure-sensitive adhesive layer, and then irradiating the pressure-sensitive adhesive with ultraviolet rays to cure the pressure-sensitive adhesive. Layers can be formed. The active energy ray-curable pressure-sensitive adhesive has a property of being cured by being irradiated with energy rays such as ultraviolet rays and electron beams. Since the activated energy ray-curable adhesive has adhesiveness even before irradiation with energy rays, it adheres to an adherend such as an optical film or a liquid crystal layer, and is cured by irradiation with energy rays to improve adhesion. A pressure-sensitive adhesive having adjustable properties.
活性エネルギー線硬化型粘着剤は、一般にはアクリル系粘着剤と、エネルギー線重合性化合物とを主成分として含む。通常はさらに架橋剤が配合されており、また必要に応じて、光重合開始剤や光増感剤等を配合することもできる。
The active energy ray-curable pressure-sensitive adhesive generally contains an acrylic pressure-sensitive adhesive and an energy ray-polymerizable compound as main components. Usually, a cross-linking agent is further blended, and if necessary, a photopolymerization initiator, a photosensitizer, or the like can be blended.
粘着剤層は、その貯蔵弾性率が23℃において0.10~10.0MPaであることが好ましく、0.15~5.0MPaであることがより好ましい。23℃における貯蔵弾性率が0.10MPa以上であると、温度変化が生じた際に剥がれ等の不具合を抑制できるため好ましい。また、10.0MPa以下であると粘着力の低下による耐久性の低下が起こりにくいため好ましい。なお、粘着剤層の貯蔵弾性率は、実施例に記載の方法によって測定することができる。
The storage elastic modulus of the pressure-sensitive adhesive layer is preferably 0.10 to 10.0 MPa, more preferably 0.15 to 5.0 MPa at 23 ° C. When the storage elastic modulus at 23 ° C. is 0.10 MPa or more, problems such as peeling can be suppressed when a temperature change occurs, which is preferable. Further, when it is 10.0 MPa or less, the durability is less likely to be lowered due to the decrease in the adhesive strength, which is preferable. The storage elastic modulus of the pressure-sensitive adhesive layer can be measured by the method described in Examples.
粘着剤層の厚みは、3μm以上であることが好ましく、5μm以上であることがより好ましい。また、粘着剤層の厚みは、40μm以下であることが好ましく、30μm以下であることがより好ましい。
The thickness of the pressure-sensitive adhesive layer is preferably 3 μm or more, and more preferably 5 μm or more. The thickness of the pressure-sensitive adhesive layer is preferably 40 μm or less, and more preferably 30 μm or less.
〔剥離フィルム〕
剥離フィルムは、粘着剤層を被覆保護する、又は、粘着剤層を支持するものであって、粘着剤層に対して剥離可能なセパレータとしての機能を有する。剥離フィルムとしては、基材フィルムの粘着剤層側の表面にシリコーン処理等の離型処理が施されたフィルムを挙げることができる。基材フィルムをなす樹脂材料としては、上記した保護層をなす樹脂材料と同様のものを挙げることができる。樹脂フィルムは1層構造であってもよく、2層以上の多層構造の多層樹脂フィルムであってもよい。 [Release film]
The release film covers and protects the pressure-sensitive adhesive layer or supports the pressure-sensitive adhesive layer, and has a function as a separator that can be peeled off from the pressure-sensitive adhesive layer. Examples of the release film include a film in which the surface of the base film on the pressure-sensitive adhesive layer side is subjected to a mold release treatment such as a silicone treatment. Examples of the resin material forming the base film include the same resin materials as those forming the protective layer described above. The resin film may have a one-layer structure or may be a multilayer resin film having a multilayer structure of two or more layers.
剥離フィルムは、粘着剤層を被覆保護する、又は、粘着剤層を支持するものであって、粘着剤層に対して剥離可能なセパレータとしての機能を有する。剥離フィルムとしては、基材フィルムの粘着剤層側の表面にシリコーン処理等の離型処理が施されたフィルムを挙げることができる。基材フィルムをなす樹脂材料としては、上記した保護層をなす樹脂材料と同様のものを挙げることができる。樹脂フィルムは1層構造であってもよく、2層以上の多層構造の多層樹脂フィルムであってもよい。 [Release film]
The release film covers and protects the pressure-sensitive adhesive layer or supports the pressure-sensitive adhesive layer, and has a function as a separator that can be peeled off from the pressure-sensitive adhesive layer. Examples of the release film include a film in which the surface of the base film on the pressure-sensitive adhesive layer side is subjected to a mold release treatment such as a silicone treatment. Examples of the resin material forming the base film include the same resin materials as those forming the protective layer described above. The resin film may have a one-layer structure or may be a multilayer resin film having a multilayer structure of two or more layers.
以下、実施例及び比較例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.
[厚みの測定]
各層の厚みは、株式会社ニコン製のデジタルマイクロメーターであるMH-15Mを用いて測定した。 [Measurement of thickness]
The thickness of each layer was measured using MH-15M, a digital micrometer manufactured by Nikon Corporation.
各層の厚みは、株式会社ニコン製のデジタルマイクロメーターであるMH-15Mを用いて測定した。 [Measurement of thickness]
The thickness of each layer was measured using MH-15M, a digital micrometer manufactured by Nikon Corporation.
[面内レタデーションの測定]
AxoScan(Axometrics,Inc.社製)を用いて、緩衝層の波長590nmにおける面内レタデーションRe(590)を測定した。 [Measurement of in-plane retardation]
In-plane retardation Re (590) at a wavelength of 590 nm of the buffer layer was measured using AxoScan (manufactured by Axometrics, Inc.).
AxoScan(Axometrics,Inc.社製)を用いて、緩衝層の波長590nmにおける面内レタデーションRe(590)を測定した。 [Measurement of in-plane retardation]
In-plane retardation Re (590) at a wavelength of 590 nm of the buffer layer was measured using AxoScan (manufactured by Axometrics, Inc.).
[引張弾性率の測定]
緩衝層として用いるフィルムから、MD長さ100mm、TD長さ20mmの長方形の測定用サンプルを切り出した。MD長さは、複合偏光板が有する直線偏光層の吸収軸方向に相当する方向の長さとした。引張試験機〔(株)島津製作所製 オートグラフ AG-Xplus試験機〕の上下つかみ具で、つかみ具の間隔が5cmとなるように測定用サンプルのMD長さ方向の両端を挟み、温度23℃、相対湿度55%の環境下、引張速度1mm/分で測定用サンプルをMD長さ方向に引っ張り、得られた応力-ひずみ曲線における初期の直線の傾きから、温度23℃、相対湿度55%でのMD長さ方向における引張弾性率〔GPa〕を算出した。 [Measurement of tensile modulus]
A rectangular measurement sample having an MD length of 100 mm and a TD length of 20 mm was cut out from the film used as the buffer layer. The MD length was defined as the length in the direction corresponding to the absorption axis direction of the linearly polarizing layer of the composite polarizing plate. With the upper and lower grippers of the tensile tester [Autograph AG-Xplus tester manufactured by Shimadzu Corporation], sandwich both ends of the measurement sample in the MD length direction so that the distance between the grippers is 5 cm, and the temperature is 23 ° C. In an environment with a relative humidity of 55%, the measurement sample was pulled in the MD length direction at a tensile speed of 1 mm / min, and from the slope of the initial straight line in the obtained stress-strain curve, the temperature was 23 ° C. and the relative humidity was 55%. The tensile elasticity [GPa] in the MD length direction was calculated.
緩衝層として用いるフィルムから、MD長さ100mm、TD長さ20mmの長方形の測定用サンプルを切り出した。MD長さは、複合偏光板が有する直線偏光層の吸収軸方向に相当する方向の長さとした。引張試験機〔(株)島津製作所製 オートグラフ AG-Xplus試験機〕の上下つかみ具で、つかみ具の間隔が5cmとなるように測定用サンプルのMD長さ方向の両端を挟み、温度23℃、相対湿度55%の環境下、引張速度1mm/分で測定用サンプルをMD長さ方向に引っ張り、得られた応力-ひずみ曲線における初期の直線の傾きから、温度23℃、相対湿度55%でのMD長さ方向における引張弾性率〔GPa〕を算出した。 [Measurement of tensile modulus]
A rectangular measurement sample having an MD length of 100 mm and a TD length of 20 mm was cut out from the film used as the buffer layer. The MD length was defined as the length in the direction corresponding to the absorption axis direction of the linearly polarizing layer of the composite polarizing plate. With the upper and lower grippers of the tensile tester [Autograph AG-Xplus tester manufactured by Shimadzu Corporation], sandwich both ends of the measurement sample in the MD length direction so that the distance between the grippers is 5 cm, and the temperature is 23 ° C. In an environment with a relative humidity of 55%, the measurement sample was pulled in the MD length direction at a tensile speed of 1 mm / min, and from the slope of the initial straight line in the obtained stress-strain curve, the temperature was 23 ° C. and the relative humidity was 55%. The tensile elasticity [GPa] in the MD length direction was calculated.
[高温耐久性試験]
実施例又は比較例で得られた複合偏光板から、MD長さ160mm、TD長さ100mmのサイズのサンプルを得、このサンプルから剥離フィルムを剥離し、露出した粘着剤層(第3粘着剤層)をガラス板に貼合して試験片とした。この試験片を、温度50℃、圧力0.5MPaで15分間、オートクレーブ処理をし、続いて、温度95℃のオーブンに500時間投入した後、試験片の輝度向上フィルム側の外観を目視で観察した。 [High temperature durability test]
From the composite polarizing plate obtained in Examples or Comparative Examples, a sample having a size of MD length of 160 mm and a TD length of 100 mm was obtained, a release film was peeled off from this sample, and an exposed pressure-sensitive adhesive layer (third pressure-sensitive adhesive layer) was obtained. ) Was attached to a glass plate to prepare a test piece. This test piece was autoclaved at a temperature of 50 ° C. and a pressure of 0.5 MPa for 15 minutes, and then placed in an oven at a temperature of 95 ° C. for 500 hours, and then the appearance of the test piece on the brightness improving film side was visually observed. did.
実施例又は比較例で得られた複合偏光板から、MD長さ160mm、TD長さ100mmのサイズのサンプルを得、このサンプルから剥離フィルムを剥離し、露出した粘着剤層(第3粘着剤層)をガラス板に貼合して試験片とした。この試験片を、温度50℃、圧力0.5MPaで15分間、オートクレーブ処理をし、続いて、温度95℃のオーブンに500時間投入した後、試験片の輝度向上フィルム側の外観を目視で観察した。 [High temperature durability test]
From the composite polarizing plate obtained in Examples or Comparative Examples, a sample having a size of MD length of 160 mm and a TD length of 100 mm was obtained, a release film was peeled off from this sample, and an exposed pressure-sensitive adhesive layer (third pressure-sensitive adhesive layer) was obtained. ) Was attached to a glass plate to prepare a test piece. This test piece was autoclaved at a temperature of 50 ° C. and a pressure of 0.5 MPa for 15 minutes, and then placed in an oven at a temperature of 95 ° C. for 500 hours, and then the appearance of the test piece on the brightness improving film side was visually observed. did.
〔実施例1〕
(直線偏光層の作製)
平均重合度約2,400、ケン化度99.9モル%以上であるポリビニルアルコールからなる厚み75μmのポリビニルアルコールフィルムを、乾式で約5倍に一軸延伸し、さらに緊張状態を保ったまま、60℃の純水に1分間浸漬した後、ヨウ素/ヨウ化カリウム/水の重量比が0.05/5/100の水溶液に28℃で60秒間浸漬した。その後、ヨウ化カリウム/ホウ酸/水の重量比が8.5/8.5/100の水溶液に72℃で300秒間浸漬した。引き続き26℃の純水で20秒間洗浄した後、65℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み28μmの直線偏光層を得た。 [Example 1]
(Preparation of linearly polarized light layer)
A 75 μm-thick polyvinyl alcohol film made of polyvinyl alcohol having an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched about 5 times by a dry method, and 60 while maintaining a tense state. After immersing in pure water at ° C. for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Subsequently, the mixture was washed with pure water at 26 ° C. for 20 seconds and then dried at 65 ° C. to obtain a linearly polarized light layer having a thickness of 28 μm in which iodine was adsorbed and oriented on polyvinyl alcohol.
(直線偏光層の作製)
平均重合度約2,400、ケン化度99.9モル%以上であるポリビニルアルコールからなる厚み75μmのポリビニルアルコールフィルムを、乾式で約5倍に一軸延伸し、さらに緊張状態を保ったまま、60℃の純水に1分間浸漬した後、ヨウ素/ヨウ化カリウム/水の重量比が0.05/5/100の水溶液に28℃で60秒間浸漬した。その後、ヨウ化カリウム/ホウ酸/水の重量比が8.5/8.5/100の水溶液に72℃で300秒間浸漬した。引き続き26℃の純水で20秒間洗浄した後、65℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み28μmの直線偏光層を得た。 [Example 1]
(Preparation of linearly polarized light layer)
A 75 μm-thick polyvinyl alcohol film made of polyvinyl alcohol having an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched about 5 times by a dry method, and 60 while maintaining a tense state. After immersing in pure water at ° C. for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Subsequently, the mixture was washed with pure water at 26 ° C. for 20 seconds and then dried at 65 ° C. to obtain a linearly polarized light layer having a thickness of 28 μm in which iodine was adsorbed and oriented on polyvinyl alcohol.
(接着剤の調製)
アセトアセチル基を含有する変性PVA系樹脂(三菱ケミカル(株)製:ゴーセネックスZ-410)50gを950gの純水に溶解し、90℃で2時間加熱後常温に冷却し、PVA溶液を得た。次いで、それぞれの化合物が下記の濃度になるように、PVA溶液、マレイン酸、グリオキサール、純水を配合し、PVA系接着剤を調製した。
PVA 3.0重量%
マレイン酸 0.01重量%
グリオキサール 0.15重量% (Adhesive preparation)
50 g of a modified PVA resin containing an acetoacetyl group (manufactured by Mitsubishi Chemical Corporation: Gosenex Z-410) was dissolved in 950 g of pure water, heated at 90 ° C. for 2 hours and then cooled to room temperature to obtain a PVA solution. .. Next, a PVA solution, maleic acid, glyoxal, and pure water were blended so that each compound had the following concentration to prepare a PVA-based adhesive.
PVA 3.0% by weight
Maleic acid 0.01% by weight
Glyoxal 0.15% by weight
アセトアセチル基を含有する変性PVA系樹脂(三菱ケミカル(株)製:ゴーセネックスZ-410)50gを950gの純水に溶解し、90℃で2時間加熱後常温に冷却し、PVA溶液を得た。次いで、それぞれの化合物が下記の濃度になるように、PVA溶液、マレイン酸、グリオキサール、純水を配合し、PVA系接着剤を調製した。
PVA 3.0重量%
マレイン酸 0.01重量%
グリオキサール 0.15重量% (Adhesive preparation)
50 g of a modified PVA resin containing an acetoacetyl group (manufactured by Mitsubishi Chemical Corporation: Gosenex Z-410) was dissolved in 950 g of pure water, heated at 90 ° C. for 2 hours and then cooled to room temperature to obtain a PVA solution. .. Next, a PVA solution, maleic acid, glyoxal, and pure water were blended so that each compound had the following concentration to prepare a PVA-based adhesive.
PVA 3.0% by weight
Maleic acid 0.01% by weight
Glyoxal 0.15% by weight
(偏光板の作製)
上記で得た直線偏光層の一方の面に上記接着剤を塗布し、第1保護層(厚み40μmのトリアセチルセルロースフィルム〔コニカミノルタオプト株式会社製の商品名「KC4UYW」〕)を貼合し、他方の面に上記接着剤を塗布し、第2保護層(厚み40μmのアクリル系樹脂フィルム〔東洋鋼鈑株式会社製の商品名「HX-40NE」〕)を貼合し、乾燥させて偏光板を作製した。これらの材料の貼合の際には、各材料の貼合面にコロナ処理を行った。 (Preparation of polarizing plate)
The above adhesive is applied to one surface of the linearly polarizing layer obtained above, and a first protective layer (a triacetyl cellulose film having a thickness of 40 μm [trade name “KC4UYW” manufactured by Konica Minolta Opto Co., Ltd.]) is attached. , The above adhesive is applied to the other surface, a second protective layer (acrylic resin film with a thickness of 40 μm [trade name “HX-40NE” manufactured by Toyo Steel Co., Ltd.]) is attached, dried and polarized. A plate was made. When these materials were bonded, a corona treatment was performed on the bonded surface of each material.
上記で得た直線偏光層の一方の面に上記接着剤を塗布し、第1保護層(厚み40μmのトリアセチルセルロースフィルム〔コニカミノルタオプト株式会社製の商品名「KC4UYW」〕)を貼合し、他方の面に上記接着剤を塗布し、第2保護層(厚み40μmのアクリル系樹脂フィルム〔東洋鋼鈑株式会社製の商品名「HX-40NE」〕)を貼合し、乾燥させて偏光板を作製した。これらの材料の貼合の際には、各材料の貼合面にコロナ処理を行った。 (Preparation of polarizing plate)
The above adhesive is applied to one surface of the linearly polarizing layer obtained above, and a first protective layer (a triacetyl cellulose film having a thickness of 40 μm [trade name “KC4UYW” manufactured by Konica Minolta Opto Co., Ltd.]) is attached. , The above adhesive is applied to the other surface, a second protective layer (acrylic resin film with a thickness of 40 μm [trade name “HX-40NE” manufactured by Toyo Steel Co., Ltd.]) is attached, dried and polarized. A plate was made. When these materials were bonded, a corona treatment was performed on the bonded surface of each material.
(複合偏光板の作製)
上記で得た偏光板の第1保護層側に、市販の厚み25μmのシート状アクリル系粘着剤を貼合して第1粘着剤層を形成し、第1粘着剤層の偏光板側とは反対側に、緩衝層としてのトリアセチルセルロースフィルム〔富士フイルム株式会社製の商品名「TJ40UL」〕を貼合した。続いて、緩衝層の第1粘着剤層側とは反対側に、市販の厚み25μmのシート状アクリル系粘着剤を貼合して第2粘着剤層を形成し、第2粘着剤層の緩衝層側とは反対側に、輝度向上フィルム(3M社製の「AFP-V3 HCS」)を貼合した。さらに、偏光板の第2保護層側に、剥離フィルム(厚み38μm、ポリエチレンテレフタレートフィルム)上に厚み25μmのアクリル系粘着剤の粘着剤層(第3粘着剤層とする。)が形成された粘着剤シートの粘着剤層側を貼合した。以上により、剥離フィルム、第3粘着剤層、偏光板(第3粘着剤層側から、第2保護層、直線偏光層、第1保護層をこの順に積層したもの)、第1粘着剤層、緩衝層、第2粘着剤層、及び輝度向上フィルムがこの順に積層された複合偏光板を得た。なお、各材料の貼合の際には、各材料の貼合面にコロナ処理を行った。 (Preparation of composite polarizing plate)
A commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 μm is bonded to the first protective layer side of the polarizing plate obtained above to form the first pressure-sensitive adhesive layer. A triacetyl cellulose film [trade name "TJ40UL" manufactured by Fujifilm Co., Ltd.] as a buffer layer was attached to the opposite side. Subsequently, a commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 μm is bonded to the side of the buffer layer opposite to the first pressure-sensitive adhesive layer side to form a second pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer is buffered. A brightness improving film (“AFP-V3 HCS” manufactured by 3M Co., Ltd.) was attached to the side opposite to the layer side. Further, on the second protective layer side of the polarizing plate, a pressure-sensitive adhesive layer (referred to as a third pressure-sensitive adhesive layer) of an acrylic pressure-sensitive adhesive having a thickness of 25 μm is formed on a release film (thickness 38 μm, polyethylene terephthalate film). The adhesive layer side of the agent sheet was bonded. As described above, the release film, the third pressure-sensitive adhesive layer, the polarizing plate (the second protective layer, the linearly polarized light layer, and the first protective layer are laminated in this order from the third pressure-sensitive adhesive layer side), the first pressure-sensitive adhesive layer, A composite polarizing plate in which a buffer layer, a second pressure-sensitive adhesive layer, and a brightness improving film were laminated in this order was obtained. At the time of bonding each material, a corona treatment was performed on the bonded surface of each material.
上記で得た偏光板の第1保護層側に、市販の厚み25μmのシート状アクリル系粘着剤を貼合して第1粘着剤層を形成し、第1粘着剤層の偏光板側とは反対側に、緩衝層としてのトリアセチルセルロースフィルム〔富士フイルム株式会社製の商品名「TJ40UL」〕を貼合した。続いて、緩衝層の第1粘着剤層側とは反対側に、市販の厚み25μmのシート状アクリル系粘着剤を貼合して第2粘着剤層を形成し、第2粘着剤層の緩衝層側とは反対側に、輝度向上フィルム(3M社製の「AFP-V3 HCS」)を貼合した。さらに、偏光板の第2保護層側に、剥離フィルム(厚み38μm、ポリエチレンテレフタレートフィルム)上に厚み25μmのアクリル系粘着剤の粘着剤層(第3粘着剤層とする。)が形成された粘着剤シートの粘着剤層側を貼合した。以上により、剥離フィルム、第3粘着剤層、偏光板(第3粘着剤層側から、第2保護層、直線偏光層、第1保護層をこの順に積層したもの)、第1粘着剤層、緩衝層、第2粘着剤層、及び輝度向上フィルムがこの順に積層された複合偏光板を得た。なお、各材料の貼合の際には、各材料の貼合面にコロナ処理を行った。 (Preparation of composite polarizing plate)
A commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 μm is bonded to the first protective layer side of the polarizing plate obtained above to form the first pressure-sensitive adhesive layer. A triacetyl cellulose film [trade name "TJ40UL" manufactured by Fujifilm Co., Ltd.] as a buffer layer was attached to the opposite side. Subsequently, a commercially available sheet-like acrylic pressure-sensitive adhesive having a thickness of 25 μm is bonded to the side of the buffer layer opposite to the first pressure-sensitive adhesive layer side to form a second pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer is buffered. A brightness improving film (“AFP-V3 HCS” manufactured by 3M Co., Ltd.) was attached to the side opposite to the layer side. Further, on the second protective layer side of the polarizing plate, a pressure-sensitive adhesive layer (referred to as a third pressure-sensitive adhesive layer) of an acrylic pressure-sensitive adhesive having a thickness of 25 μm is formed on a release film (thickness 38 μm, polyethylene terephthalate film). The adhesive layer side of the agent sheet was bonded. As described above, the release film, the third pressure-sensitive adhesive layer, the polarizing plate (the second protective layer, the linearly polarized light layer, and the first protective layer are laminated in this order from the third pressure-sensitive adhesive layer side), the first pressure-sensitive adhesive layer, A composite polarizing plate in which a buffer layer, a second pressure-sensitive adhesive layer, and a brightness improving film were laminated in this order was obtained. At the time of bonding each material, a corona treatment was performed on the bonded surface of each material.
緩衝層として用いたトリアセチルセルロースフィルムの波長590nmにおける面内レタデーションRe(590)を測定したところ、0.5nmであった。温度23℃、相対湿度55%における緩衝層の引張弾性率は、5200MPaであった。また、得られた複合偏光板について、高温耐久性試験を行ったところ、輝度向上フィルムにシワの発生が見られず、複合偏光板の外観は良好であった。
The in-plane retardation Re (590) of the triacetyl cellulose film used as the buffer layer at a wavelength of 590 nm was measured and found to be 0.5 nm. The tensile elastic modulus of the buffer layer at a temperature of 23 ° C. and a relative humidity of 55% was 5200 MPa. Further, when the obtained composite polarizing plate was subjected to a high temperature durability test, no wrinkles were observed on the brightness improving film, and the appearance of the composite polarizing plate was good.
〔比較例1〕
緩衝層及び第2粘着剤層を設けないこと以外は、実施例1と同様にして、剥離フィルム、第3粘着剤層、偏光板(第3粘着剤層側から、第2保護層、直線偏光層、第1保護層をこの順に積層したもの)、第1粘着剤層、及び輝度向上フィルムがこの順に積層された複合偏光板を得た。得られた複合偏光板について、高温耐久性試験を行ったところ、輝度向上フィルムの長辺側の端部に細かなシワが多数確認された。 [Comparative Example 1]
A release film, a third pressure-sensitive adhesive layer, and a polarizing plate (from the third pressure-sensitive adhesive layer side, a second protective layer, linearly polarized light) in the same manner as in Example 1 except that a buffer layer and a second pressure-sensitive adhesive layer are not provided. A composite polarizing plate in which a layer, a first protective layer were laminated in this order), a first pressure-sensitive adhesive layer, and a brightness improving film were laminated in this order was obtained. When the obtained composite polarizing plate was subjected to a high temperature durability test, many fine wrinkles were confirmed at the end on the long side of the brightness improving film.
緩衝層及び第2粘着剤層を設けないこと以外は、実施例1と同様にして、剥離フィルム、第3粘着剤層、偏光板(第3粘着剤層側から、第2保護層、直線偏光層、第1保護層をこの順に積層したもの)、第1粘着剤層、及び輝度向上フィルムがこの順に積層された複合偏光板を得た。得られた複合偏光板について、高温耐久性試験を行ったところ、輝度向上フィルムの長辺側の端部に細かなシワが多数確認された。 [Comparative Example 1]
A release film, a third pressure-sensitive adhesive layer, and a polarizing plate (from the third pressure-sensitive adhesive layer side, a second protective layer, linearly polarized light) in the same manner as in Example 1 except that a buffer layer and a second pressure-sensitive adhesive layer are not provided. A composite polarizing plate in which a layer, a first protective layer were laminated in this order), a first pressure-sensitive adhesive layer, and a brightness improving film were laminated in this order was obtained. When the obtained composite polarizing plate was subjected to a high temperature durability test, many fine wrinkles were confirmed at the end on the long side of the brightness improving film.
1,2 複合偏光板、5,6 液晶表示装置、10 偏光板、11 直線偏光層、12 第1保護層、13 第2保護層 15a,15b 緩衝層、18 輝度向上フィルム、31 第1粘着剤層、32 第2粘着剤層、33 第3粘着剤層、35 剥離フィルム、41 液晶セル、42 バックライト。
1, 2, composite polarizing plate, 5, 6 liquid crystal display device, 10 polarizing plate, 11 linear polarizing layer, 12 first protective layer, 13 second protective layer 15a, 15b buffer layer, 18 brightness improving film, 31 first adhesive Layer, 32 second adhesive layer, 33 third adhesive layer, 35 release film, 41 liquid crystal cell, 42 backlight.
Claims (14)
- 直線偏光層の少なくとも片面に保護層を有する偏光板と、輝度向上フィルムと、を有する複合偏光板であって、
前記偏光板の前記保護層側に、第1粘着剤層、緩衝層、及び前記輝度向上フィルムがこの順に積層されており、
前記緩衝層の温度23℃、相対湿度55%における引張弾性率は、1.5GPa以上である、複合偏光板。 A composite polarizing plate having a polarizing plate having a protective layer on at least one side of the linearly polarizing layer and a brightness improving film.
The first pressure-sensitive adhesive layer, the buffer layer, and the brightness improving film are laminated in this order on the protective layer side of the polarizing plate.
A composite polarizing plate having a tensile elastic modulus of 1.5 GPa or more at a temperature of 23 ° C. and a relative humidity of 55% of the buffer layer. - 前記緩衝層と前記輝度向上フィルムとは、第2粘着剤層を介して貼合されている、請求項1に記載の複合偏光板。 The composite polarizing plate according to claim 1, wherein the buffer layer and the brightness improving film are bonded to each other via a second pressure-sensitive adhesive layer.
- 前記緩衝層は、樹脂フィルムである、請求項1又は2に記載の複合偏光板。 The composite polarizing plate according to claim 1 or 2, wherein the buffer layer is a resin film.
- 前記樹脂フィルムは、セルロースエステル系樹脂、(メタ)アクリル酸系樹脂、及び環状オレフィン系樹脂からなる群より選ばれる少なくとも1種の樹脂からなるフィルムを含む、請求項3に記載の複合偏光板。 The composite polarizing plate according to claim 3, wherein the resin film includes a film made of at least one resin selected from the group consisting of a cellulose ester resin, a (meth) acrylic acid resin, and a cyclic olefin resin.
- 前記緩衝層は、前記輝度向上フィルムに直接接している、請求項1に記載の複合偏光板。 The composite polarizing plate according to claim 1, wherein the buffer layer is in direct contact with the brightness improving film.
- 前記緩衝層は、硬化性成分を含む樹脂組成物の硬化物層である、請求項1又は5に記載の複合偏光板。 The composite polarizing plate according to claim 1 or 5, wherein the buffer layer is a cured product layer of a resin composition containing a curable component.
- 前記硬化性成分は、活性エネルギー線硬化性化合物を含む、請求項6に記載の複合偏光板。 The composite polarizing plate according to claim 6, wherein the curable component contains an active energy ray-curable compound.
- 前記緩衝層の波長590nmにおける面内レタデーションRe(590)は、20nm以下である、請求項1~7のいずれか1項に記載の複合偏光板。 The composite polarizing plate according to any one of claims 1 to 7, wherein the in-plane retardation Re (590) of the buffer layer at a wavelength of 590 nm is 20 nm or less.
- 前記第1粘着剤層は、前記偏光板の前記保護層と前記緩衝層とを貼合している、請求項1~8のいずれか1項に記載の複合偏光板。 The composite polarizing plate according to any one of claims 1 to 8, wherein the first pressure-sensitive adhesive layer is a bonding layer of the protective layer of the polarizing plate and the buffer layer.
- 前記偏光板は、前記直線偏光層の両面に前記保護層を有する、請求項1~9のいずれか1項に記載の複合偏光板。 The composite polarizing plate according to any one of claims 1 to 9, wherein the polarizing plate has the protective layers on both sides of the linearly polarizing layer.
- 前記偏光板の前記輝度向上フィルム側とは反対側に、第3粘着剤層を有する、請求項1~10のいずれか1項に記載の複合偏光板。 The composite polarizing plate according to any one of claims 1 to 10, which has a third pressure-sensitive adhesive layer on the side of the polarizing plate opposite to the brightness improving film side.
- 前記第3粘着剤層の前記偏光板側とは反対側に剥離フィルムを有する、請求項11に記載の複合偏光板。 The composite polarizing plate according to claim 11, which has a release film on the side of the third pressure-sensitive adhesive layer opposite to the polarizing plate side.
- 請求項1~12のいずれか1項に記載の複合偏光板と、液晶セルと、を有する液晶表示装置。 A liquid crystal display device comprising the composite polarizing plate according to any one of claims 1 to 12 and a liquid crystal cell.
- さらに、バックライトを有し、
前記複合偏光板は、前記液晶セルと前記バックライトとの間に、前記輝度向上フィルム側が前記バックライト側となるように配置されている、請求項13に記載の液晶表示装置。 In addition, it has a backlight,
The liquid crystal display device according to claim 13, wherein the composite polarizing plate is arranged between the liquid crystal cell and the backlight so that the brightness improving film side is the backlight side.
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