CN116661045A - Laminate, optical film, polarizing plate, and image display device - Google Patents
Laminate, optical film, polarizing plate, and image display device Download PDFInfo
- Publication number
- CN116661045A CN116661045A CN202310147716.3A CN202310147716A CN116661045A CN 116661045 A CN116661045 A CN 116661045A CN 202310147716 A CN202310147716 A CN 202310147716A CN 116661045 A CN116661045 A CN 116661045A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal layer
- organic substrate
- film
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- 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
-
- 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
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
-
- 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
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/55—Liquid crystals
-
- 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
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a laminate, an optical film, a polarizing plate and an image display device, wherein the laminate comprises a liquid crystal layer and 2 substrates, and the 2 substrates can be easily peeled off in a prescribed order. A laminate comprising, in order, a 1 st organic substrate, a 1 st liquid crystal layer, a 2 nd liquid crystal layer, and a 2 nd organic substrate, wherein the peel force P1 between the 1 st organic substrate and the 1 st liquid crystal layer and the peel force P2 between the 2 nd organic substrate and the 2 nd liquid crystal layer satisfy a predetermined relationship, and the 2 nd liquid crystal layer contains a polymer, and the unevenness calculated by a unevenness calculating method is 3.0 or more.
Description
Technical Field
The invention relates to a laminate, an optical film, a polarizing plate and an image display device.
Background
Use of a liquid crystal layer formed using a liquid crystal compound for an optical film used in the field of displays.
Patent document 1 discloses an optical film having a base material and a liquid crystal layer provided adjacently on the base material, wherein the liquid crystal layer is formed without providing an alignment film. More specifically, patent document 1 discloses that by using a polymer that can be unevenly distributed at the interface of a substrate, it is possible to achieve high alignment of a liquid crystal compound in a liquid crystal layer without providing an alignment film, and to easily peel the liquid crystal layer from the substrate.
Patent document 1: international publication No. 2018/174194
Meanwhile, in recent years, when a liquid crystal layer is bonded to various members, a laminate in which a releasable substrate is disposed on both sides of the liquid crystal layer is sometimes used. Specifically, after one substrate (light release substrate) of the laminate is peeled off, the peeled surface is bonded to the object to be bonded, and then the other substrate (heavy release substrate) is peeled off, so that the liquid crystal layer is bonded to the object to be bonded. In the case of using such a laminate, it is preferable that the peeling of the heavy release substrate is suppressed at the time of peeling of the light release substrate, and that the peelability of the 2 sheets of substrates is excellent. That is, it is preferable that 2 substrates contained in the laminate be easily peeled in a predetermined order.
The present inventors have found that when the optical film including the substrate and the liquid crystal layer described in patent document 1 is used as a part of the laminate, one of the substrates is less likely to be peeled off, and further improvement is required.
Disclosure of Invention
In view of the above-described circumstances, an object of the present invention is to provide a laminate which comprises a liquid crystal layer and 2 substrates and in which the 2 substrates can be easily peeled in a predetermined order.
The present invention also provides an optical film, a polarizing plate, and an image display device.
The present inventors have repeatedly studied in order to solve the above problems, and as a result, have completed the present invention having the following structure.
(1) A laminate comprising, in order, a 1 st organic substrate, a 1 st liquid crystal layer, a 2 nd liquid crystal layer, and a 2 nd organic substrate,
the peel force P1 between the 1 st organic substrate and the 1 st liquid crystal layer and the peel force P2 between the 2 nd organic substrate and the 2 nd liquid crystal layer satisfy the relationship of the following formula (A),
the 2 nd liquid crystal layer comprises a polymer,
the unevenness obtained by the unevenness calculating method described later was 3.0 or more.
(2) The laminate according to (1), wherein the unevenness is 100 or less.
(3) The laminate according to (1) or (2), wherein the peel force P1 and the peel force P2 satisfy the relationship of the following formula (B).
(4) The laminate according to any one of (1) to (3), wherein the 2 nd liquid crystal layer is in direct contact with the 2 nd organic substrate.
(5) The laminate according to any one of (1) to (4), wherein an adhesive layer or an adhesive layer is provided between the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
(6) The laminate according to any one of (1) to (5), wherein a 3 rd liquid crystal layer is provided between the 1 st liquid crystal layer and the 2 nd liquid crystal layer,
the 2 nd liquid crystal layer is in direct contact with the 3 rd liquid crystal layer.
(7) The laminate according to any one of (1) to (6), wherein the elastic modulus of the polymer is 0.01 to 0.30GPa.
(8) The laminate according to any one of (1) to (7), wherein the polymer contains a repeating unit represented by the following formula (1).
(9) The laminate according to (8), wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2).
(10) An optical film obtained by peeling the 1 st organic substrate and the 2 nd organic substrate from the laminate according to any one of (1) to (9).
(11) A polarizing plate having the optical film according to (10).
(12) An image display device having the polarizing plate of (11).
Effects of the invention
According to the present invention, a laminate including a liquid crystal layer and 2 substrates can be provided, and the 2 substrates can be easily peeled in a predetermined order.
Further, according to the present invention, an optical film, a polarizing plate, and an image display device can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of an embodiment of a laminate of the present invention.
Fig. 2 is a diagram for explaining a step of bonding the 1 st liquid crystal layer and the 2 nd liquid crystal layer in the laminate of the present invention to an object to be bonded.
Fig. 3 is a diagram for explaining a step of bonding the 1 st liquid crystal layer and the 2 nd liquid crystal layer in the laminate of the present invention to an object to be bonded.
Fig. 4 is a diagram for explaining a step of bonding the 1 st liquid crystal layer and the 2 nd liquid crystal layer in the laminate of the present invention to an object to be bonded.
Fig. 5 shows an example of a secondary ion intensity distribution from a polymer obtained by time-of-flight secondary ion mass spectrometry.
Detailed Description
The present invention will be described in detail below.
The constituent elements described below can be described according to the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range indicated by "to" refers to a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value.
In the present specification, "(meth) acrylic acid" is used in the meaning of "either or both of acrylic acid and methacrylic acid".
In the present invention, re (λ) and Rth (λ) represent in-plane retardation at wavelength λ and retardation in the thickness direction, respectively. When not specifically described, the wavelength λ was 550nm.
In the present invention, re (λ) and Rth (λ) are values measured at wavelength λ by AxoScan (manufactured by Axometrics corporation). The average refractive index ((nx+ny+nz)/3) and film thickness (d (. Mu.m)) were calculated by inputting with AxScan
Slow axis direction (°)
Re(λ)＝R0(λ)
Rth(λ)＝((nx+ny)/2-nz)×d。
In addition, R0 (λ) is shown as a value calculated with AxoScan, representing Re (λ).
In this specification, regarding refractive indices nx, ny, and nz, an abbe refractometer (NAR-4T, manufactured by ATAGO co., ltd. And the like) was used, and measurement was performed using a sodium lamp (λ=589 nm) as a light source. In the case of measuring the wavelength dependence, the measurement can be performed by using a combination of a multi-wavelength abbe refractometer DR-M2 (manufactured by atanoco., ltd.) and an interference filter.
And, the polymer manual (JOHN WILEY & SONS, INC) and various optical film catalogue values can be used. The values of the average refractive index of the primary optical film are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) and polystyrene (1.59).
The term "light" in the present specification means actinic rays or radiation, for example, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light: extreme Ultraviolet), X-rays, ultraviolet rays, electron beams (EB: electron Beam), and the like. Among them, ultraviolet rays are preferable.
The bonding direction of the 2-valent group (e.g., -COO-) described in the present specification is not particularly limited, and is, for example, "L 1 -L 2 -L 3 "in the bond L 2 In the case of-CO-O-, if it is to be combined with L 1 The position of the side bond is 1 to be bonded with L 3 The position of the side bond is set to 2, then L 2 May be 1-CO-O-2, or 1-O-CO-2.
The characteristic point of the laminate of the present invention is to adjust the unevenness of the polymer described later. The present inventors studied the reason why the peeling property of the substrate is poor in patent document 1, and found that the peeling property is related to the uneven amount of the polymer. More specifically, in patent document 1, the amount of unevenness of the polymer on the releasable substrate side in the liquid crystal layer adjacent to the releasable substrate is small (in other words, the unevenness described later is small), and as a result, the peeling force of the substrate and the liquid crystal layer is large, and the peeling property of the substrate is poor. In contrast, the present inventors have found that the effects of the present invention can be obtained by adjusting the degree of unevenness of the polymer within a predetermined range.
Fig. 1 shows an example of a laminate of the present invention.
As shown in fig. 1, the laminate 10 includes, in order, a 1 st organic substrate 12, a 1 st liquid crystal layer 14, a 2 nd liquid crystal layer 16, and a 2 nd organic substrate 18. The 2 nd liquid crystal layer 16 contains a polymer described later, and exhibits predetermined unevenness.
In fig. 1, the 1 st organic substrate 12 is in direct contact with the 1 st liquid crystal layer 14, and the 2 nd liquid crystal layer 16 is also in direct contact with the 2 nd organic substrate 18.
In fig. 1, the 1 st liquid crystal layer 14 is in direct contact with the 2 nd liquid crystal layer 16, but as will be described later, the laminate may have a 3 rd liquid crystal layer between the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
As will be described later, the laminate may have an adhesive layer or an adhesive layer between the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
The laminate 10 is used for bonding liquid crystal layers (1 st liquid crystal layer 14 and 2 nd liquid crystal layer 16) to an object to be bonded (for example, a polarizer). As a bonding step, first, as shown in fig. 2, the 1 st organic base material 12 is peeled from the laminate 10. At this time, the 2 nd organic substrate 18 is preferably not peeled off. Next, as shown in fig. 3, the 1 st liquid crystal layer 14 side of the laminate obtained by peeling the 1 st organic base material 12 is bonded to the adherend 20. Then, as shown in fig. 4, the 1 st liquid crystal layer 14 and the 2 nd liquid crystal layer 16 are bonded to the object 20 by peeling the 2 nd organic substrate 18.
As shown in the above steps, the 1 st organic substrate 12 functions as a so-called light release substrate, and the 2 nd organic substrate 18 functions as a so-called heavy release substrate.
In the present invention, the peeling of the substrates shown in fig. 2 to 4 can be easily performed in a predetermined order (in other words, the peeling property is good) by adjusting the peeling force P1 between the 1 st organic substrate 12 and the 1 st liquid crystal layer 14 and the peeling force P2 between the 2 nd organic substrate 18 and the 2 nd liquid crystal layer 16 to a predetermined range and setting the unevenness described later to a predetermined range.
In particular, by adjusting the unevenness to be described later to a predetermined range, the 2 nd organic substrate 18 can be easily peeled off.
The following describes the formula (a) and the unevenness in detail first, and then describes the respective members in the laminate in detail.
Relationship of peel force
In the laminate of the present invention, the peel force P1 between the 1 st organic substrate and the 1 st liquid crystal layer and the peel force P2 between the 2 nd organic substrate and the 2 nd liquid crystal layer satisfy the relationship of formula (a).
Formula (A) P1 < P2
By satisfying the above relation, when the 1 st organic substrate is peeled off, peeling of the 2 nd organic substrate can be suppressed, and the 1 st organic substrate and the 2 nd organic substrate can be peeled off sequentially and orderly.
In addition, from the viewpoint of further suppressing peeling of the 2 nd organic substrate and easily peeling the 1 st organic substrate, it is preferable that the peeling force P1 and the peeling force P2 satisfy the relationship of the formula (B).
The formula (B) P1/P2 is less than or equal to 0.80
Among them, P1/P2 is preferably 0.75 or less, more preferably 0.65 or less. The lower limit is not particularly limited, but is preferably 0.30 or more, more preferably 0.45 or more.
The magnitude of the peeling force P1 is not particularly limited, but is preferably 0.03 to 0.20N/25mm, more preferably 0.06 to 0.15N/25mm.
The magnitude of the peeling force P2 is not particularly limited, but is preferably 0.05 to 0.30N/25mm, more preferably 0.10 to 0.20N/25mm.
The above-mentioned peel force P1 can be calculated by a 180 ° peel test using a so-called tensile tester.
As an example of the method for calculating the peeling force P1, an evaluation sample composed of the 1 st organic substrate and the 1 st liquid crystal layer in the laminate may be prepared separately to calculate the peeling force P1. More specifically, an evaluation sample composed of the 1 st organic base material and a part of the 1 st liquid crystal layer in the laminate was prepared, the surface of the 1 st liquid crystal layer side of the evaluation sample was subjected to corona treatment, and the ultraviolet curable adhesive composition was applied to the surface of the 1 st liquid crystal layer subjected to corona treatment to form a coating film. Next, the substrate and the evaluation sample were bonded so that the formed coating film was in contact with the substrate (e.g., polarizer), and the coating film was cured by irradiation with ultraviolet light. Next, an adhesive layer was disposed on the substrate side surface of the obtained evaluation sample with a substrate, a predetermined size (width 25mm×length 150 mm) was cut out from the obtained evaluation sample with an adhesive layer, and the adhesive layer of the cut-out evaluation sample was bonded to a glass substrate. Then, a release tape (width 25 mm. Times. Length 180 mm) was attached to the surface of the 1 st organic substrate side of the evaluation sample attached to the glass substrate. Then, one end of the release tape was gripped by a tensile tester, and a release test was performed at a crosshead speed of 5 m/min and a release angle of 180 ° under an atmosphere having a relative humidity of 60% at a temperature of 25 ℃, whereby a release force P1 between the 1 st organic substrate and the 1 st liquid crystal layer was calculated. The peeling force P1 corresponds to the peeling force at which the peeling force becomes stable until the peeling of the 1 st organic substrate from the 1 st liquid crystal layer is completed by lifting the peeling tape.
In the above description, a method of preparing an evaluation sample separately was described, but the peeling force P1 may be calculated by applying a peeling tape to the 1 st organic substrate of the laminate according to the above procedure and performing the above 180 ° test.
The peel force P2 may be calculated by the same procedure as the peel force P1. More specifically, an evaluation sample composed of the 2 nd organic substrate and the 2 nd liquid crystal layer portion in the laminate may be prepared separately, and the peel force P2 may be calculated by the above-described method.
In the above description, a method of preparing an evaluation sample separately is described, but the peeling force P2 may be calculated by applying the peeling tape to the 2 nd organic substrate in the laminate after peeling the 1 st organic substrate from the laminate according to the above procedure and performing the 180 ° test.
In addition, it is preferable that the 1 st liquid crystal layer and the 2 nd liquid crystal layer are hardly peeled off from each other. That is, it is preferable that the peeling force between the 1 st liquid crystal layer and the 2 nd liquid crystal layer is more difficult than the peeling force between the 1 st liquid crystal layer and the 1 st organic base material and the peeling force between the 2 nd liquid crystal layer and the 2 nd organic base material, and more specifically, the peeling force between the 1 st liquid crystal layer and the 2 nd liquid crystal layer is larger than the peeling force P1 and the peeling force P2.
In the case where the laminated body has the 3 rd liquid crystal layer between the 1 st liquid crystal layer and the 2 nd liquid crystal layer, the peeling force between the 1 st liquid crystal layer and the 3 rd liquid crystal layer and the peeling force between the 2 nd liquid crystal layer and the 3 rd liquid crystal layer are preferably larger than the peeling force P1 and the peeling force P2.
< unevenness >)
The 2 nd liquid crystal layer in the laminate of the present invention contains a polymer, and the unevenness obtained by the unevenness calculating method described later is 3.0 or more.
The above-mentioned unevenness indicates the degree of uneven distribution of the polymer in the 2 nd liquid crystal layer to the 2 nd organic substrate side, and the larger the value thereof, the more uneven the polymer in the 2 nd liquid crystal layer is distributed to the 2 nd organic substrate side.
Hereinafter, the unevenness calculating method will be described in detail.
First, the secondary ion intensity from the polymer in the 2 nd liquid crystal layer was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS) while irradiating an ion beam from the 2 nd organic substrate side surface of the 2 nd liquid crystal layer to the surface opposite to the 1 st liquid crystal layer side surface. Examples of the type of ion beam include an ion beam generated by an argon cluster ion gun (Ar-GCIB gun).
The TOF-SIMS may be capable of obtaining a profile of the 2 nd liquid crystal layer in the depth direction, or may be capable of performing analysis of the depth direction of both the 2 nd organic substrate and the 2 nd liquid crystal layer on the 2 nd liquid crystal layer side while irradiating an ion beam from the surface of the 2 nd organic substrate in the laminate.
FIG. 5 shows an example of a secondary ion intensity distribution from a polymer obtained by TOF-SIMS analysis. The horizontal axis represents the distance (depth position) from the 2 nd organic substrate side surface of the 2 nd liquid crystal layer, and the vertical axis represents the intensity of the secondary ion from the polymer. In fig. 5, a position having a horizontal axis of 0 corresponds to the surface of the 2 nd liquid crystal layer on the 2 nd organic substrate side, a depth position corresponding to 20% of the total thickness of the 2 nd liquid crystal layer from the surface of the 2 nd organic substrate side is represented as a depth position D20, and a depth position corresponding to 50% of the total thickness of the 2 nd liquid crystal layer from the surface of the 2 nd organic substrate side is represented as a depth position D50. Depth position D20 and depth position D50 correspond to the positions shown in fig. 1.
Although not shown in fig. 5, when the 2 nd liquid crystal layer is formed by applying the 2 nd liquid crystal layer forming composition containing a polymer to the 2 nd organic substrate, a part of the polymer may be immersed in the 2 nd organic substrate due to the influence of the solvent contained in the 2 nd liquid crystal layer forming composition.
A baseline was drawn for the obtained depth profile, and a reference of the secondary ion intensity was determined.
Then, the region from the 2 nd organic substrate side surface of the 2 nd liquid crystal layer to the depth position D20 is referred to as a surface layer region R1, the region from the depth position D20 to the depth position D50 is referred to as an inner region R2, and the maximum value I of the secondary ion intensity from the polymer in the surface layer region R1 A1 Average value I of secondary ion intensity from polymer in inner region R2 A2 The ratio is set to be non-uniformity.
Further, the average value I is calculated by averaging the secondary ion intensities from the polymer in the depth direction in the internal region R2 for the 1 st second ion beam irradiation time A2 。
The unevenness is 3.0 or more. Among them, from the viewpoint of more excellent releasability of the 2 nd organic substrate, the unevenness is preferably 5.0 or more, more preferably 10.0 or more. When the unevenness is less than 3.0, the amount of unevenness of the polymer is small, and as a result, the peeling property of the 2 nd organic substrate is poor.
The upper limit of the unevenness is not particularly limited, and is usually 150 or less, preferably 100 or less, more preferably 50.0 or less, and still more preferably 30.0 or less. When the unevenness is 100 or less, the peeling force of the 2 nd organic substrate increases, and as a result, peeling of the 2 nd organic substrate is suppressed when the 1 st organic substrate is peeled.
The method for adjusting the unevenness is not particularly limited, and a method for adjusting conditions at the time of forming the 2 nd liquid crystal layer may be mentioned. For example, when the 2 nd liquid crystal layer is formed by applying the 2 nd liquid crystal layer forming composition containing a polymer onto the 2 nd organic substrate, the unevenness can be adjusted by adjusting the compatibility of the solvent contained in the 2 nd liquid crystal layer forming composition with the 2 nd organic substrate and the polymer. More specifically, when a solvent having high compatibility with the 2 nd organic substrate and the polymer is selected, the solvent easily permeates into the 2 nd organic substrate, and as a result, the polymer easily becomes unevenly distributed on the 2 nd organic substrate side. When the 2 nd liquid crystal layer is formed by applying the 2 nd liquid crystal layer-forming composition containing a polymer to the 2 nd organic substrate, the unevenness can be adjusted by adjusting the drying time after the 2 nd liquid crystal layer-forming composition is applied. More specifically, if the drying time is prolonged, the time for the polymer to flow in the coating film becomes long, and as a result, the polymer tends to be unevenly distributed to the 2 nd organic substrate side.
As described later, by introducing a group that easily interacts with the 2 nd organic base material into the polymer, the polymer can be easily unevenly distributed toward the 2 nd organic base material, and as a result, unevenness can be improved.
Hereinafter, each member constituting the laminate will be described in detail.
< 1 st organic substrate >
The 1 st organic substrate is a member for supporting the 1 st liquid crystal layer. The 1 st organic substrate is a releasable substrate (pseudo support) released from the laminate.
The 1 st organic base material may be made of an organic material, and a resin base material is preferable.
As a material of the resin base material, a cellulose polymer; acrylic polymers such as polymethyl methacrylate and acrylate polymers as lactone ring-containing polymers; thermoplastic norbornene-based polymers; a polycarbonate-based polymer; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; polyolefin polymers such as polyethylene, polypropylene and ethylene/propylene copolymers; vinyl chloride-based polymers; amide polymers such as nylon and aromatic polyamide; imide-based polymers; a sulfone polymer; polyether sulfone-based polymers; polyether-ether-ketone polymers; polyphenylene sulfide-based polymers; vinylidene chloride polymers; a vinyl alcohol polymer; vinyl butyral based polymers; an aryl ester polymer; polyoxymethylene polymers; an epoxy polymer; or a polymer obtained by mixing these polymers.
Among them, as a material of the resin base material, triacetyl cellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable, and triacetyl cellulose is more preferable.
The 1 st organic substrate may contain various additives (e.g., an optical anisotropy adjuster, a wavelength dispersion adjuster, microparticles, a plasticizer, an ultraviolet inhibitor, a degradation inhibitor, a release agent, etc.).
The 1 st organic substrate may have a single-layer structure or a multilayer structure.
When the 1 st organic substrate has a multilayer structure, the substrate may have a structure including a support and an alignment film.
The support may be the resin base material.
The alignment film may be formed by rubbing treatment of an organic compound (preferably a polymer), oblique evaporation of an inorganic compound, formation of a layer having micro grooves, or accumulation of an organic compound (e.g., ω -tricosanoic acid, dioctadecyl methyl ammonium chloride, methyl stearate) based on langmuir-blodgett method (LB film).
As the alignment film, a photo-alignment film can be also mentioned.
The thickness of the alignment film is not particularly limited as long as the alignment function can be exhibited, and is preferably 0.01 to 5.0. Mu.m, more preferably 0.05 to 3.0. Mu.m, and still more preferably 0.5 to 1.0. Mu.m.
The thickness of the 1 st organic substrate is not particularly limited, but is preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m, still more preferably 20 to 90. Mu.m.
< 1 st liquid crystal layer >)
The 1 st liquid crystal layer is a layer disposed on the 1 st organic substrate. The 1 st liquid crystal layer is a layer obtained by aligning a liquid crystal compound, and has optical anisotropy. That is, the 1 st liquid crystal layer is an optically anisotropic layer.
The 1 st liquid crystal layer is preferably a layer in which an aligned liquid crystal compound is fixed. In the case where the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by a curing treatment described later.
In addition, the "fixed" state is a state in which the orientation of the liquid crystal compound is maintained. Specifically, the following states are preferable: the layer generally has no fluidity in a temperature range of-30 to 70 ℃ under a more severe condition of 0 to 50 ℃ and is free from change in orientation morphology due to external field or external force, and can stably and continuously maintain a state of a fixed orientation morphology.
The state of alignment (alignment state) of the liquid crystal compound is not particularly limited, and a known alignment state can be given. Examples of the alignment state include a uniform alignment, a homeotropic alignment, a hybrid alignment, a cholesteric alignment, a twisted alignment, and an oblique alignment. The twisted alignment means an alignment state in which the liquid crystal compound is twisted from one main surface to the other main surface of the liquid crystal layer with the thickness direction of the liquid crystal layer as an axis of rotation. In the twist alignment, the twist angle of the liquid crystal compound (twist angle of the alignment direction of the liquid crystal compound) is usually more than 0 ° and 360 ° or less.
Liquid crystal compounds are generally classified into a rod type and a disk type according to their shapes. Furthermore, there are low molecular types and high molecular types, respectively. The polymer generally means a molecule having a polymerization degree of 100 or more (physical/phase transition kinetics of polymer, well-known, page 2, rock bookstore, 1992). In the present invention, any liquid crystal compound may be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound is preferable. And, a monomer or a lower molecular weight liquid crystal compound having a degree of polymerization of less than 100 is preferable.
The liquid crystal compound preferably has a polymerizable group. That is, the liquid crystal compound is preferably a polymerizable liquid crystal compound. Examples of the polymerizable group included in the liquid crystal compound include an acryl group, a methacryl group, an epoxy group, and a vinyl group.
By polymerizing such a polymerizable liquid crystal compound, the orientation of the liquid crystal compound can be fixed. In addition, the liquid crystal compound is not required to exhibit liquid crystallinity after being fixed by polymerization.
The rod-like liquid crystal compound is preferably a compound described in, for example, claim 1 of JP-A11-513019 or paragraphs [0026] to [0098] of JP-A2005-289980, and the discotic liquid crystal compound is preferably a compound described in, for example, paragraphs [0020] to [0067] of JP-A2007-108732 or paragraphs [0013] to [0108] of JP-A2010-244038.
As the liquid crystal compound, a liquid crystal compound having reverse wavelength dispersibility can be used.
In this specification, the term "reverse wavelength dispersibility" of a liquid crystal compound means that when the retardation (Re) value in the plane at a specific wavelength (visible light range) of a retardation film produced using the compound is measured, the Re value becomes equal or higher as the measured wavelength increases.
The 1 st liquid crystal layer is preferably a layer obtained by fixing a vertically aligned discotic liquid crystal compound. Of these, the 1 st liquid crystal layer is more preferably a layer formed by fixing a vertically aligned discotic liquid crystal compound having a polymerizable group by polymerization.
More specifically, the above-mentioned layer obtained by fixing a vertically aligned discotic liquid crystal compound means a layer obtained by fixing a discotic liquid crystal compound having a vertically aligned optical axis (axis orthogonal to the disk surface) aligned in the same direction.
The state in which the discotic liquid crystal compound is vertically aligned means that the discotic face of the discotic liquid crystal compound is parallel to the thickness direction of the layer. The angle between the disk surface and the layer thickness direction is preferably in the range of 0 to 20 °, more preferably in the range of 0 to 10 °.
The state in which the optical axes (axes orthogonal to the disk surface) of the discotic liquid crystal compounds are aligned in the same orientation is not necessarily strictly the same orientation, but means that the maximum difference in slow axis orientation among 20 slow axis orientations (the difference between 2 slow axis orientations in which the difference is the largest among 20 slow axis orientations) is smaller than 10 ° when the slow axis orientation is measured at any 20 positions in the surface.
The retardation in-plane of the 1 st liquid crystal layer at a wavelength of 550nm is not particularly limited, but is preferably 120 to 240nm, more preferably 130 to 230nm.
The retardation of the 1 st liquid crystal layer in the thickness direction at a wavelength of 550nm is not particularly limited, but is preferably-120 to-60 nm, more preferably-115 to-65 nm.
The average thickness of the 1 st liquid crystal layer is not particularly limited, and is preferably 10 μm or less, more preferably 0.1 to 5.0 μm, and still more preferably 0.3 to 2.0 μm.
The average thickness is obtained by measuring the thickness of the 1 st liquid crystal layer at 5 or more points and arithmetically averaging the thicknesses.
< 2 nd liquid crystal layer >)
The 2 nd liquid crystal layer is a layer disposed on the 2 nd organic substrate. The 2 nd liquid crystal layer is a layer obtained by aligning a liquid crystal compound, and has optical anisotropy. That is, the 2 nd liquid crystal layer is an optically anisotropic layer.
Further, the 1 st liquid crystal layer and the 2 nd liquid crystal layer are different layers.
The 2 nd liquid crystal layer is preferably a layer in which an aligned liquid crystal compound is fixed. In the case where the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by a curing treatment described later.
The liquid crystal compound is as described in the 1 st liquid crystal layer.
The state of alignment (alignment state) of the liquid crystal compound is not particularly limited, and examples thereof include the alignment state exemplified in the 1 st liquid crystal layer.
The 2 nd liquid crystal layer is preferably a layer obtained by fixing a vertically aligned rod-like liquid crystal compound. Among them, the 2 nd liquid crystal layer is more preferably a layer formed by fixing a rod-like liquid crystal compound having a polymerizable group in a vertical alignment by polymerization.
The state in which the rod-like liquid crystal compound is vertically aligned means that the long axis of the rod-like liquid crystal compound is parallel to the thickness direction of the 2 nd liquid crystal layer. The angle between the long axis of the rod-like liquid crystal compound and the thickness direction of the 2 nd liquid crystal layer is not necessarily strictly parallel, but is preferably in the range of 0 to 20 °, more preferably in the range of 0 to 10 °.
The retardation of the 2 nd liquid crystal layer in the thickness direction at a wavelength of 550nm is not particularly limited, but is preferably-120 to-10 nm, more preferably-100 to-30 nm.
The average thickness of the 2 nd liquid crystal layer is not particularly limited, but is preferably 10 μm or less, more preferably 0.1 to 5.0 μm, and still more preferably 0.3 to 2.0 μm.
The average thickness is obtained by measuring the thickness of the 2 nd liquid crystal layer at 5 or more points and arithmetically averaging them.
The 2 nd liquid crystal layer comprises the polymer.
From the viewpoint of more excellent releasability of the 1 st organic substrate and/or the 2 nd organic substrate (hereinafter, also simply referred to as "viewpoint of more excellent effect of the present invention"), the polymer preferably has a group selected from the group consisting of a hydrogen-bonding group, a group having a salt structure, and a boric acid group (-B (OH) 2 ) An interactive group of the group consisting of a borate group and a group represented by the formula (X). When the polymer has the above-mentioned interactive group, it is liable to interact with the 2 nd organic substrate, and as a result, the polymer is liable to be unevenly distributed to the 2 nd organic substrate side.
Formula (X): -O-CO-R
Examples of the hydrogen bonding group include a hydroxyl group, a thiol group, a carboxyl group, an amino group, an amide group, a urea group, and a urethane group.
A group having a salt structure refers to a group having a structure derived from a salt including an anion derived from an acid and a cation derived from a base. Examples of the salt structure include a carboxylate structure, a sulfonate structure, a phosphonate structure, and a quaternary ammonium structure.
In the formula (X), R represents an alkyl group having 1 to 20 carbon atoms. Wherein, in the case of an alkyl group having 2 to 20 carbon atoms, the-CH group constituting the alkyl group 2 More than 1 of them may also be substituted by-COO-or-CO-.
The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5.
* Indicating the bonding location.
From the viewpoint of more excellent effects of the present invention, the polymer preferably contains a repeating unit having an interactive group.
Among them, the repeating unit having an interactive group is preferably a repeating unit represented by formula (1).
In the formula (1), R 1 Represents a hydrogen atom or a methyl group.
L 1 Representation sheetBond or is selected from-O-, -CO-, -NR 3 -a 2-valent aliphatic group that may have a substituent, a 2-valent aromatic group that may have a substituent, and a 2-valent linking group of a group consisting of combinations thereof. R is R 3 Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
As the 2-valent aliphatic group, an alkylene group is preferable.
The number of carbon atoms of the 2-valent aliphatic group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
As the above combination, there may be mentioned-COO-, -CONR 3 -, -COO-a 2-valent aliphatic group which may have a substituent-and-CONR 3 -a 2-valent aliphatic group which may have a substituent-and the like.
R 2 Represents an alkyl group having 1 to 20 carbon atoms. Wherein, in the case of an alkyl group having 2 to 20 carbon atoms, the-CH group constituting the alkyl group 2 More than 1 of them may also be substituted by-COO-or-CO-.
The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5.
The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (2).
In the formula (2), R 2 Represents a hydrogen atom or a methyl group.
The content of the repeating unit having an interactive group in the polymer is not particularly limited, but is preferably 40 to 95% by mass, more preferably 60 to 90% by mass, based on the total repeating units in the polymer, from the viewpoint of further excellent effects of the present invention.
From the viewpoint of more excellent alignment properties of the liquid crystal compound, the polymer preferably contains a repeating unit having an active hydrogen-containing group.
Among them, the repeating unit having an active hydrogen-containing group is preferably a repeating unit represented by the formula (3).
In the formula (3), R 5 Represents a hydrogen atom or a methyl group.
L 2 represents-O-or-NH-.
R 6 Represents an active hydrogen-containing group. The active hydrogen-containing group preferably contains a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, a sulfo group, a mercapto group, and an imino group (hereinafter, also referred to as a "specific group"), and more preferably contains a hydroxyl group.
The active hydrogen-containing group is preferably an aliphatic hydrocarbon group having a specific group, and more preferably an aliphatic hydrocarbon group having a hydroxyl group.
The number of specific groups in the aliphatic hydrocarbon having specific groups is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.
The number of carbon atoms of the aliphatic hydrocarbon having a specific group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
The content of the repeating unit having an active hydrogen-containing group in the polymer is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, based on the total repeating units in the polymer, from the viewpoint of further excellent effects of the present invention.
The polymer preferably comprises the above-described repeating units having interactive groups and repeating units having active hydrogen-containing groups.
The polymer may also contain repeating units other than those having interactive groups and those having active hydrogen-containing groups.
The weight average molecular weight (Mw) of the polymer is not particularly limited, and is usually 5000 to 500000, and more preferably 20000 to 100000 from the viewpoint of further excellent effects of the present invention.
The weight average molecular weight and the number average molecular weight in the present invention are values measured by a Gel Permeation Chromatography (GPC) method under the conditions shown below.
Solvent (eluent): THF (tetrahydrofuran)
Device name: TOSOH HLC-8320GPC
Column: use of 3 pieces of TOSOH TSKgel Super HZM-H (4.6 mm. Times.15 cm) connected
Column temperature: 40 DEG C
Sample concentration: 0.1 mass%
Flow rate: 1.0ml/min
Calibration curve: TSK standard polystyrene manufactured by TOSOH uses a calibration curve of 7 samples with mw=2800000 to 1050 (Mw/mn=1.03 to 1.06)
The elastic modulus of the polymer is not particularly limited, but is preferably 0.01 to 0.30GPa, and among them, from the viewpoint of further excellent effects of the present invention, it is more preferably 0.04 to 0.15GPa, and further preferably 0.06 to 0.12GPa.
As a method for measuring the elastic modulus of a polymer, the following method can be mentioned: a layer (thickness 20 μm) including a polymer as a measurement object was prepared, and the elastic modulus of a polymer film measured using a nanoindenter TI-950 (using a spherical indenter of 1 μm with an indentation load of 5 mN) manufactured by HYSITRON was measured, and this value was taken as the elastic modulus of the polymer.
The content of the polymer in the 2 nd liquid crystal layer is not particularly limited, but is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% based on the total mass of the 2 nd liquid crystal layer, from the viewpoint of further excellent effects of the present invention.
< 2 nd organic substrate >
Is the component for supporting the 2 nd liquid crystal layer. The 2 nd organic substrate is a releasable substrate (pseudo support) released from the laminate.
The mode of the 2 nd organic substrate is the same as that of the 1 st organic substrate, and therefore, the description thereof is omitted.
< other parts >)
The laminate may contain components other than the 1 st organic substrate, the 1 st liquid crystal layer, the 2 nd liquid crystal layer, and the 2 nd organic substrate.
(3 rd liquid Crystal layer)
The laminate may have a 3 rd liquid crystal layer between the 1 st liquid crystal layer and the 2 nd liquid crystal layer. The 3 rd liquid crystal layer is a layer different from the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
The 3 rd liquid crystal layer is preferably a layer in which an aligned liquid crystal compound is fixed. In the case where the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by a curing treatment described later.
The liquid crystal compound is as described in the 1 st liquid crystal layer.
The state of alignment (alignment state) of the liquid crystal compound is not particularly limited, and examples thereof include the alignment state exemplified in the 1 st liquid crystal layer.
The 3 rd liquid crystal layer is preferably a layer obtained by fixing a rod-like liquid crystal compound which is twist-aligned along a helical axis extending in the thickness direction. Among them, the 3 rd liquid crystal layer is more preferably a layer formed by polymerization fixation of a rod-like liquid crystal compound having a polymerizable group which is twist-aligned along a helical axis extending in the thickness direction.
The twist angle of the rod-like liquid crystal compound (twist angle in the alignment direction of the liquid crystal compound) is not particularly limited, and is usually more than 0 ° and 360 ° or less, and from the viewpoint of further excellent effects of the present invention, it is preferably in the range of 80±30° (in the range of 50 to 110 °), more preferably in the range of 80±20° (in the range of 60 to 100 °).
In addition, regarding the method of measuring the twist angle, an AxoScan (polarimeter) device from Axometrics was used, and the measurement was performed using device analysis software from Axometrics.
The twist alignment of the rod-like liquid crystal compound means that the rod-like liquid crystal compound is twisted from one main surface to the other main surface of the 3 rd liquid crystal layer with the thickness direction of the 3 rd liquid crystal layer as an axis. At the same time, the alignment direction (in-plane slow axis direction) of the rod-like liquid crystal compound differs depending on the position in the thickness direction of the 3 rd liquid crystal layer.
In the twist alignment, the long axis of the rod-like liquid crystal compound is preferably arranged parallel to the main surface of the 3 rd liquid crystal layer. The angle between the long axis of the rod-like liquid crystal compound and the main surface of the 3 rd liquid crystal layer is preferably in the range of 0 to 20 °, more preferably in the range of 0 to 10 °.
The value of the product Δnd of the refractive index anisotropy Δn of the 3 rd liquid crystal layer and the thickness d of the 3 rd liquid crystal layer at a wavelength of 550nm is not particularly limited, and is preferably 120 to 240nm, more preferably 130 to 230nm.
Regarding the above-described measurement method of Δnd, axoScan (polarimeter) apparatus from Axometrics was used, and the measurement was performed using apparatus analysis software from Axometrics.
When the 1 st liquid crystal layer is a layer in which a vertically aligned discotic liquid crystal compound is fixed and the 3 rd liquid crystal layer is a layer in which a rod-like liquid crystal compound which is twist-aligned along a helical axis extending in the thickness direction is fixed, the angle between the in-plane slow axis of the 1 st liquid crystal layer and the in-plane slow axis of the 3 rd liquid crystal layer on the 1 st liquid crystal layer side surface is preferably in the range of 0 to 20 °.
The average thickness of the 3 rd liquid crystal layer is not particularly limited, and is preferably 10 μm or less, more preferably 0.1 to 5.0 μm, and still more preferably 0.3 to 2.0 μm.
The average thickness is obtained by measuring the thickness of the 3 rd liquid crystal layer at 5 or more points and arithmetically averaging them.
(adhesive layer and adhesive layer)
The laminate may have an adhesive layer or an adhesive layer between the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
The adhesive layer may be a known adhesive layer. The adhesive layer is formed by, for example, applying an ultraviolet-curable adhesive to form a coating film, and curing the coating film by irradiation with ultraviolet rays.
As the pressure-sensitive adhesive layer, a known pressure-sensitive adhesive layer can be used.
When the laminate has the 3 rd liquid crystal layer, the laminate may have an adhesive layer or an adhesive layer between the 1 st liquid crystal layer and the 3 rd liquid crystal layer.
When the laminate has the 3 rd liquid crystal layer, the laminate may have an adhesive layer or an adhesive layer between the 2 nd and 3 rd liquid crystal layers.
< manufacturing method >)
The method for producing the laminate is not particularly limited as long as the laminate having the above characteristics can be produced. Among them, from the viewpoint of excellent productivity of the laminate, a method for producing the laminate having the following steps 1 to 3 is preferable.
Step 1: a1 st film comprising a 1 st organic substrate and a 1 st liquid crystal layer is obtained by applying a 1 st liquid crystal layer-forming composition containing a liquid crystal compound having a polymerizable group to the 1 st organic substrate to form a 1 st composition layer, aligning the liquid crystal compound in the 1 st composition layer, and then subjecting the 1 st composition layer to a curing treatment.
Step 2: a2 nd film comprising a 2 nd organic substrate and a 2 nd liquid crystal layer is obtained by applying a 2 nd composition for forming a 2 nd liquid crystal layer comprising a liquid crystal compound having a polymerizable group and a polymer to a 2 nd organic substrate, aligning the liquid crystal compound in the 2 nd composition layer, and then subjecting the 2 nd composition layer to a curing treatment.
And step 3: the 1 st film and the 2 nd film were laminated so that the 1 st liquid crystal layer in the 1 st film and the 2 nd liquid crystal layer in the 2 nd film were opposed to each other, thereby obtaining a laminate. The steps of steps 1 to 3 will be described in detail below.
(Process 1)
The step 1 is as follows: the 1 st composition layer is formed by coating the 1 st composition for forming a 1 st liquid crystal layer on the 1 st organic substrate, and after aligning the liquid crystal compound in the 1 st composition layer, the 1 st composition layer is subjected to a curing treatment to obtain a 1 st film comprising the 1 st organic substrate and the 1 st liquid crystal layer.
The 1 st liquid crystal layer forming composition contains a liquid crystal compound having a polymerizable group. The liquid crystal compounds are as described above.
The content of the liquid crystal compound having a polymerizable group in the 1 st liquid crystal layer-forming composition is preferably 60 to 99% by mass, more preferably 70 to 98% by mass, based on the total solid content of the 1 st liquid crystal layer-forming composition.
The solid component means a component capable of forming the 1 st liquid crystal layer from which the solvent is removed, and the property is set to be a solid component even if the liquid is in a liquid state.
The 1 st liquid crystal layer-forming composition may contain a compound other than the liquid crystal compound having a polymerizable group.
For example, the 1 st liquid crystal layer-forming composition may contain a chiral agent for the purpose of twist-aligning the liquid crystal compound. The chiral agent is added to twist-orient the liquid crystal compound, and it is needless to say that the chiral agent is not added in the case of a compound exhibiting optical activity such as asymmetric carbon in a molecule of the liquid crystal compound. Furthermore, depending on the manufacturing method and the twist angle, the addition of a chiral agent is not required.
The chiral agent is not particularly limited in structure as long as it is compatible with the liquid crystal compound to be used. Any of known chiral reagents (for example, those described in chapter 3, chapter 4 to 3, pages 199 and 1989, the code "handbook of liquid crystal devices" by the committee 142 of Japan Society for the Promotion of Science) may be used.
The amount of chiral agent used is not particularly limited and may be adjusted to achieve the above twist angle.
The 1 st liquid crystal layer-forming composition may contain a polymerization initiator. The polymerization initiator used is selected according to the form of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
The content of the polymerization initiator in the 1 st liquid crystal layer-forming composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, relative to the total solid content of the 1 st liquid crystal layer-forming composition.
Other components that may be contained in the 1 st liquid crystal layer-forming composition include, in addition to the above, polyfunctional monomers, alignment control agents (vertical alignment agents, horizontal alignment agents), surfactants, adhesion modifiers, plasticizers, and solvents.
Examples of the coating method of the composition for forming a liquid crystal layer 1 include curtain coating, dip coating, spin coating, print coating, spray coating, slit coating, roll coating, slide coating, doctor blade coating, gravure coating, and bar coating.
After the composition for forming the 1 st liquid crystal layer is applied, a drying treatment may be performed as needed.
The treatment (alignment treatment) for aligning the liquid crystal compound in the formed composition 1 is not particularly limited, and a method of heating the composition 1 layer is preferable.
The conditions for heating the 1 st composition layer are not particularly limited, but the heating temperature is preferably 50 to 250 ℃, more preferably 50 to 150 ℃, and the heating time is preferably 10 seconds to 10 minutes.
After heating the 1 st composition layer, the 1 st composition layer may be cooled as needed before a solidification process (light irradiation process) described later.
The method of curing the composition layer 1 is not particularly limited, and examples thereof include a light irradiation treatment and a heat treatment. Among them, from the viewpoint of manufacturing suitability, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable.
The irradiation condition of the light irradiation treatment is not particularly limited, but is preferably 50 to 1000mJ/cm 2 Is used for the irradiation amount of the light source.
The atmosphere at the time of the light irradiation treatment is not particularly limited, and a nitrogen atmosphere is preferable.
(Process 2)
The step 2 is as follows: the 2 nd composition layer is formed by coating the 2 nd composition for forming a liquid crystal layer on the 2 nd organic substrate, and after aligning the liquid crystal compound in the 2 nd composition layer, the 2 nd composition layer is subjected to a curing treatment to obtain a 2 nd film comprising the 2 nd organic substrate and the 2 nd liquid crystal layer.
The 2 nd liquid crystal layer forming composition contains a liquid crystal compound having a polymerizable group. The liquid crystal compounds are as described above.
The content of the liquid crystal compound having a polymerizable group in the 2 nd liquid crystal layer-forming composition is preferably 60 to 99% by mass, more preferably 70 to 98% by mass, based on the total solid content of the 2 nd liquid crystal layer-forming composition.
The solid component means a component capable of forming the 2 nd liquid crystal layer from which the solvent is removed, and the property is set to be a solid component even if the liquid is in a liquid state.
The 2 nd liquid crystal layer forming composition contains a polymer. The mode of the polymer is as described in the above-mentioned liquid crystal layer 2.
The content of the polymer in the 2 nd liquid crystal layer forming composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total solid content of the 2 nd liquid crystal layer forming composition.
The 2 nd liquid crystal layer-forming composition may contain a compound other than the liquid crystal compound having a polymerizable group and the polymer.
The other component may be contained in the 1 st liquid crystal layer-forming composition.
The solvent contained in the 2 nd liquid crystal layer-forming composition is preferably selected in consideration of compatibility with the 2 nd organic base material and the polymer.
For example, when the 2 nd organic substrate is a cellulose acylate film, for example, since the compatibility of methyl ethyl ketone with cellulose acylate is excellent, the unevenness can be improved by increasing the content of methyl ethyl ketone.
The step of the method for forming the 2 nd liquid crystal layer using the 2 nd liquid crystal layer forming composition is the same as the step of the method for forming the 1 st liquid crystal layer using the 1 st liquid crystal layer forming composition in step 1, and therefore, the description thereof is omitted.
(step 3)
The step 3 is as follows: the 1 st film and the 2 nd film were laminated so that the 1 st liquid crystal layer in the 1 st film and the 2 nd liquid crystal layer in the 2 nd film were opposed to each other, thereby obtaining a laminate.
In the case of bonding the 1 st film and the 2 nd film, the bonding is preferably performed through the adhesive layer or the pressure-sensitive adhesive layer.
When an adhesive layer is used, for example, an adhesive is applied to the 1 st liquid crystal layer side surface of the 1 st film, and the 1 st film and the 2 nd film are bonded by bringing the adhesive-applied surface into contact with the 2 nd liquid crystal layer of the 2 nd film, and curing treatment is performed, whereby a desired laminate is obtained. When the adhesive is an ultraviolet-curable adhesive, the curing treatment may be an ultraviolet irradiation treatment.
When the adhesive layer is used as the adhesive layer, for example, an adhesive is applied to the 1 st liquid crystal layer side surface of the 1 st film, and the 1 st film and the 2 nd film are bonded by bringing the adhesive-applied surface into contact with the 2 nd liquid crystal layer of the 2 nd film, thereby obtaining a desired laminate.
When the laminate has the 3 rd liquid crystal layer, the following methods are given as the method for producing the laminate: in step 2, a 3 rd liquid crystal layer is further formed on the formed 2 nd liquid crystal layer to form a 3 rd film, and the 1 st film and the 3 rd film are bonded so that the 1 st liquid crystal layer in the 1 st film and the 3 rd liquid crystal layer in the 3 rd film face each other, thereby obtaining a laminate.
The step of forming the 3 rd liquid crystal layer is not particularly limited, and the following methods may be mentioned: a3 rd composition layer is formed by applying a 3 rd liquid crystal layer forming composition containing a liquid crystal compound having a polymerizable group onto a 2 nd liquid crystal layer, aligning the liquid crystal compound in the 3 rd composition layer, and then curing the 3 rd composition layer.
Further, the rubbing treatment may be performed on the 2 nd liquid crystal layer before the 3 rd liquid crystal layer forming composition is applied on the 2 nd liquid crystal layer.
The 2 nd liquid crystal layer may contain a photo-alignment compound, and the photo-alignment compound on the surface of the 2 nd liquid crystal layer may be subjected to a photo-alignment treatment before the 3 rd liquid crystal layer forming composition is applied to the 2 nd liquid crystal layer, thereby imparting alignment control ability to the surface of the 2 nd liquid crystal layer.
< optical film >)
By peeling the 1 st organic substrate and the 2 nd organic substrate from the laminate, an optical film including the 1 st liquid crystal layer and the 2 nd liquid crystal layer can be manufactured.
The optical film of the present invention can function as a so-called lambda/4 plate.
The λ/4 plate is a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and refers to a plate (optically anisotropic layer) whose in-plane retardation Re (λ) at a specific wavelength λnm satisfies Re (λ) =λ/4.
The expression may be realized at any wavelength (e.g., 550 nm) in the visible light region, and it is preferable that the in-plane retardation Re (550) at a wavelength of 550nm satisfies a relationship of 110 nm.ltoreq.Re (550). Ltoreq.180 nm.
< polarizer >
The optical film of the present invention can be used as a polarizer in combination with a polarizer, and is preferably used as a circularly polarizing plate. The circularly polarizing plate is an optical element that converts unpolarized light into circularly polarized light.
The polarizing plate of the present invention having the above-described structure is preferably used for antireflection applications of display devices such as liquid crystal display devices (LCDs), plasma Display Panels (PDPs), electroluminescent displays (ELDs), and cathode-ray tube display devices (CRTs).
The polarizer may be any member having a function of converting natural light into specific linearly polarized light, and examples thereof include an absorption type polarizer.
The type of polarizer is not particularly limited, and commonly used polarizers may be used, and examples thereof include iodine polarizers, dye polarizers using a dichroic substance, and multi-polarizing polarizers. Iodine polarizers and dye polarizers are generally produced by allowing polyvinyl alcohol to adsorb iodine or a dichroic dye and stretching the adsorbed iodine or dichroic dye.
In addition, a protective film may be disposed on one or both sides of the polarizer.
The relation between the absorption axis of the polarizer and the arrangement of the optical film is not particularly limited, and an optimal arrangement is selected according to the type of the liquid crystal layer contained in the optical film.
For example, when the 1 st liquid crystal layer in the optical film is a negative a plate, the angle formed by the absorption axis of the polarizer and the in-plane slow axis of the negative a plate is preferably in the range of 45 to 135 °.
The polarizing plate may have other members than the optical film and the polarizer of the present invention.
The polarizing plate may have an adhesive layer or an adhesive layer between the optical film of the present invention and the polarizer.
The polarizing plate may have a polymer film between the optical film of the present invention and the polarizer, but from the viewpoint of thickness reduction, it is preferable that the polarizing plate not have a polymer film. Examples of the polymer film include cellulose acylate films.
The method for producing the polarizing plate is not particularly limited, and a known method can be used.
For example, a method of bonding a polarizer to an optical film via an adhesive layer or an adhesive layer is mentioned.
< image display device >)
The optical film and the polarizing plate of the present invention can be preferably applied to an image display device.
The image display device of the present invention has the display element, the optical film, or the polarizing plate.
When the optical film of the present invention is applied to an image display device, it is preferably used as a circularly polarizing plate. In this case, the circular polarizer is disposed on the viewing side, and in the circular polarizer, the polarizer is disposed on the viewing side.
The display element is not particularly limited, and an organic electroluminescent display element and a liquid crystal display element are exemplified.
Examples
Hereinafter, the present invention will be further described in detail with reference to examples. The materials, amounts used, proportions, treatment contents, treatment steps and the like shown in the following examples may be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.
Example 1 >
(alkali saponification treatment of cellulose acylate film)
After passing a long cellulose acylate film (TD 80UL, manufactured by FUJIFILM Corporation) through a dielectric heating roller having a temperature of 60℃to raise the film surface temperature to 40℃an alkali solution having the composition shown below was applied in a coating amount of 14ml/m using a bar coater 2 Coated on the belt side of the film and transported under a steam far infrared heater manufactured by LIMITED for 10 seconds by NORITAKE co. Next, the resulting film was coated with 3ml/m pure water using a bar coater 2 . Next, the obtained film was repeatedly subjected to 3 timesAfter washing with water and dehydration with an air knife with a jet coater, the cellulose acylate film was dried by transporting to a drying zone at 70 ℃ for 10 seconds, and thus produced.
(formation of alignment film 1)
An alignment film coating liquid 1 having the following composition was continuously coated on the alkali-saponification-treated surface of the cellulose acylate film using a bar of # 14. Then, the obtained coating film was dried with warm air at 60℃for 60 seconds and then with warm air at 100℃for 120 seconds, to obtain an alignment film 1.
Modified polyvinyl alcohol (numerical values in each repeating unit represent content (mass%) with respect to the total repeating units)
(formation of 1 st liquid Crystal layer)
The alignment film 1 produced as described above was subjected to a rubbing treatment continuously. At this time, the longitudinal direction of the long film (cellulose acylate film) was parallel to the conveying direction, and the angle formed between the longitudinal direction of the film (conveying direction) and the rotation axis of the rubbing roller was set to 76 °. When the longitudinal direction (conveying direction) of the film is set to 90 ° and the clockwise direction is expressed by a positive value with respect to the film width direction (0 °) as viewed from the film side, the rotation axis of the rubbing roller is located at-14 °. In other words, the position of the rotation axis of the rubbing roller is a position rotated clockwise by 76 ° with respect to the longitudinal direction of the film, as viewed from the film side.
A1 st liquid crystal layer-forming composition (A1) containing a discotic liquid crystal compound having the following composition was applied onto the alignment film subjected to the rubbing treatment using a die coater, to form a composition layer.Then, the resultant composition layer was heated with warm air at 110℃for 2 minutes for drying the solvent and orientation curing of the discotic liquid crystalline compound. Next, the resultant composition layer was subjected to UV irradiation at 80℃to obtain a composition layer (500 mJ/cm 2 ) The 1 st liquid crystal layer (A1) was formed by immobilizing the alignment of the discotic liquid crystal compound, and A1 st film comprising the 1 st organic substrate (cellulose acylate film+alignment film 1) and the 1 st liquid crystal layer was produced.
The average thickness of the 1 st liquid crystal layer (A1) was 1.3. Mu.m. And an in-plane retardation at a wavelength of 550nm was 168nm. The average tilt angle of the discotic liquid-crystalline compound disk surface with respect to the film surface was found to be 90 °, and the discotic liquid-crystalline compound disk surface was oriented perpendicularly to the film surface.
The angle of the in-plane slow axis of the 1 st liquid crystal layer (A1) is parallel to the rotation axis of the rubbing roller, and when the width direction of the film is 0 ° (90 ° counterclockwise and-90 ° clockwise in the longitudinal direction), the in-plane slow axis direction of the 1 st liquid crystal layer (A1) is-14 ° when viewed from the 1 st liquid crystal layer (A1) side.
Discotic liquid crystalline compound 1
Discotic liquid crystalline compound 2
Interfacial orientation agent 1 for orientation film
Fluorine-containing compound A (in the following formula, a and b represent the content (mass%) of each repeating unit relative to the total repeating units, a represents 90 mass%, b represents 10 mass%. And the weight average molecular weight is 15000.)
Fluorochemical B (numerical value in each repeating unit represents content (mass%) with respect to the total repeating units) and having a weight-average molecular weight of 12500.)
Fluorochemical C (numerical value in each repeating unit represents content (mass%) with respect to the total repeating units) and has a weight-average molecular weight of 12800
[ chemical formula 10]
(production of cellulose acylate film 1)
The following composition was put into a mixing tank and stirred, and heated at 90℃for 10 minutes. Then, the obtained composition was filtered using a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, thereby preparing a dope. The solid content concentration of the concentrate was 23.5 mass%, and the concentrate solvent was methylene chloride/methanol/butanol=81/18/1 (mass ratio).
[ chemical formula 11]
[ chemical formula 12]
The dope prepared in the above was cast using a roll laminator. After casting the dope from the die so as to be in contact with the metal support cooled to 0 ℃, the resulting web (film) was peeled off. In addition, the drum is made of SUS.
When the web (film) obtained by casting is peeled from the drum and then conveyed, the web is dried in the tenter device at 30 to 40 ℃ for 20 minutes using the tenter device which carries the web while sandwiching both ends thereof with clips. Subsequently, the sheet was post-dried by zone heating while being roll-fed. The obtained web was subjected to knurling treatment and then wound up.
The film thickness of the obtained cellulose acylate film 1 was 40. Mu.m.
(formation of liquid Crystal layer 2)
A composition layer was formed by applying a 2 nd liquid crystal layer-forming composition (C1) containing a rod-like liquid crystal compound having the following composition to the cellulose acylate film 1 produced as described above using a die coater. Then, both ends of the film were held, a cooling plate (9 ℃) was provided on the side of the film on which the coating film was formed so that the distance from the film became 5mm, and a heater (75 ℃) was provided on the opposite side of the film on which the coating film was formed so that the distance from the film became 5mm, and the film was dried for 14 seconds.
Next, the obtained film was heated at 60℃for 1 minute by warm air, and was subjected to an atmosphere in which the oxygen concentration was 100 ppm by volume or less by purging with nitrogen gas, and irradiated with 100mJ/cm of irradiation light using a 365nm UV-LED 2 Is a ultraviolet ray of (a). Then, the obtained coating film was annealed with warm air at 120 ℃ for 1 minute, thereby forming a 2 nd liquid crystal layer (C1).
The obtained 2 nd liquid crystal layer (C1) was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through a wire grid polarizer at room temperature, 7.9mJ/cm 2 (wavelength: 313 nm), thereby forThe surface imparts orientation control capabilities.
The film thickness of the 2 nd liquid crystal layer (C1) formed was 0.7. Mu.m. The in-plane retardation at wavelength 550nm was 0nm, and the retardation in the thickness direction at wavelength 550nm was-80 nm. It was confirmed that the long axis direction of the rod-like liquid crystal compound was oriented perpendicularly to the film surface at an average tilt angle of 90 ° to the film surface.
/>
The rod-like liquid crystal compound (A) (hereinafter, a mixture of the compounds)
[ chemical formula 13]
Polymerization initiator S-1
[ chemical formula 14]
Photoacid generator D-1
[ chemical formula 15]
Polymer M-1 (numerical value in each repeating unit represents content (mass%) with respect to all repeating units) and has a weight average molecular weight of 58000 and a polymer elastic modulus of 0.09GPa
[ chemical formula 16]
Vertical alignment agent S01
[ chemical formula 17]
Photo-alignment polymer A-1 (the numerical value described in each repeating unit represents the content (mass%) of each repeating unit relative to the total repeating units), and has a weight-average molecular weight of 78000.)
[ chemical formula 18]
(formation of liquid Crystal layer 3)
Next, a composition (B1) for forming a 3 rd liquid crystal layer containing a rod-like liquid crystal compound having the following composition was applied onto the 2 nd liquid crystal layer (C1) produced in the above-mentioned manner by using a die coater, and heated with warm air at 80 ℃ for 60 seconds. Next, the resultant composition layer was subjected to UV irradiation at 80℃to obtain a composition layer (500 mJ/cm 2 ) The alignment of the liquid crystal compound was immobilized to form a 3 rd liquid crystal layer (B1).
The average thickness of the 3 rd liquid crystal layer (B1) was 1.3. Mu.m, Δnd at a wavelength of 550nm was 176nm, and the twist angle of the liquid crystal compound was 87 °. If the width direction of the film is 0 ° (the length direction is 90 °), the air side is 8 ° and the side contacting the 2 nd liquid crystal layer (C1) is 95 ° in the in-plane slow axis direction (alignment axis angle of the liquid crystal compound) when viewed from the 3 rd liquid crystal layer (B1).
The in-plane slow axis direction of the 2 nd liquid crystal layer is negative when the substrate is viewed from the front surface side of the 2 nd liquid crystal layer with respect to the width direction of the substrate (0 °), and positive when the substrate is counterclockwise (left turn).
Left twist chiral agent (L1)
[ chemical formula 19]
By the above steps, a laminate (B1-C1) in which the 2 nd liquid crystal layer (C1) and the 3 rd liquid crystal layer (B1) were directly laminated on the long cellulose acylate film 1 was produced. That is, the 2 nd film having the 2 nd organic substrate (cellulose acylate film 1), the 2 nd liquid crystal layer, and the 3 rd liquid crystal layer was produced.
(production of laminate)
The surface side of the 1 st liquid crystal layer (A1) formed on the produced long-shaped 1 st organic substrate (cellulose acylate film and alignment film) and the surface side of the 3 rd liquid crystal layer (B1) of the laminate (B1-C1) formed on the produced long-shaped 2 nd organic substrate (cellulose acylate film) were subjected to 1 treatment using a corona treatment apparatus under conditions of an output of 0.3kW and a treatment speed of 7.6 m/min.
Next, an ultraviolet curable adhesive composition 1 was applied to the surface side of the 1 st liquid crystal layer (A1), an adhesive composition layer was formed, and the surface side of the 3 rd liquid crystal layer (B1) of the laminate (B1-C1) formed on the 2 nd organic substrate (cellulose acylate film, 40 μm) was bonded to the adhesive composition layer so that the longitudinal direction of the film of the 1 st liquid crystal layer (A1) was parallel to the longitudinal direction of the film of the 3 rd liquid crystal layer (B1).
Next, the obtained laminate was irradiated with a high-pressure mercury lamp at an irradiation dose of 600mJ/cm 2 Ultraviolet rays (365 nm wavelength) cure the adhesive composition layer to form an adhesive layer. Thus, a laminate (a-B1-C1) was obtained in which the 1 st organic base material, the 1 st liquid crystal layer (A1), the 3 rd liquid crystal layer (B1), the 2 nd liquid crystal layer (C1), and the 2 nd organic base material were laminated in this order.
2 nd liquid crystal layer-forming composition (C2)
Example 3 >
A laminate was produced in the same manner as in example 1, except that the 2 nd liquid crystal layer of example 1 was produced as follows (formation of the 2 nd liquid crystal layer).
(formation of liquid Crystal layer 2)
A composition layer was formed by applying a 2 nd liquid crystal layer-forming composition (C3) containing a rod-like liquid crystal compound having the following composition to the cellulose acylate film 1 produced as described above using a die coater. Then, both ends of the film were held, a cooling plate (9 ℃) was provided on the side of the film on which the coating film was formed so that the distance from the film became 5mm, and a heater (75 ℃) was provided on the opposite side of the film on which the coating film was formed so that the distance from the film became 5mm, and the film was dried for 60 seconds.
Next, the obtained film was heated at 60℃for 1 minute by warm air, and was subjected to an atmosphere in which the oxygen concentration was 100 ppm by volume or less by purging with nitrogen gas, and irradiated with 100mJ/cm of irradiation light using a 365nm UV-LED 2 Is a ultraviolet ray of (a). Then, the obtained coating film was annealed with warm air at 120 ℃ for 1 minute, thereby forming a 2 nd liquid crystal layer (C3).
The obtained 2 nd liquid crystal layer (C3) was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through a wire grid polarizer at room temperature, 7.9mJ/cm 2 (wavelength: 313 nm) to impart orientation control ability to the surface.
The film thickness of the 2 nd liquid crystal layer (C3) formed was 0.7. Mu.m. The in-plane retardation at wavelength 550nm was 0nm, and the retardation in the thickness direction at wavelength 550nm was-80 nm. It was confirmed that the long axis direction of the rod-like liquid crystal compound was oriented perpendicularly to the film surface at an average tilt angle of 90 ° to the film surface.
Example 4 >
A laminate was produced in the same manner as in example 1 except that the composition (C1) for forming a 2 nd liquid crystal layer in example 1 was changed to the composition (C4) for forming a 2 nd liquid crystal layer.
Example 5 >
A laminate was produced in the same manner as in example 1, except that the polymer M-1 of example 1 was changed to the following polymer M-2.
Polymer M-2 (numerical value in each repeating unit represents content (mass%) with respect to all repeating units) and has a weight average molecular weight of 10000 and a polymer elastic modulus of 0.02GPa
[ chemical formula 20]
Example 6 >
A laminate was produced in the same manner as in example 1, except that the polymer M-1 of example 1 was changed to the following polymer M-3.
Polymer M-3 (numerical value in each repeating unit represents content (mass%) with respect to all repeating units) and having a weight average molecular weight of 200000 and a polymer elastic modulus of 0.18GPa
[ chemical formula 21]
Example 7 >
(formation of liquid Crystal layer 2)
The composition (C1) for forming the 2 nd liquid crystal layer was applied to the cellulose acylate film 1 produced in example 1 using a die coater, to form a composition layer. Then, both ends of the film were held, a cooling plate (9 ℃) was provided on the side of the film on which the coating film was formed so that the distance from the film became 5mm, and a heater (75 ℃) was provided on the opposite side of the film on which the coating film was formed so that the distance from the film became 5mm, and the film was dried for 14 seconds.
Next, the obtained film was heated at 60℃for 1 minute by warm air, and was subjected to an atmosphere in which the oxygen concentration was 100 ppm by volume or less by purging with nitrogen gas, and irradiated with 100mJ/cm of irradiation light using a 365nm UV-LED 2 Is a ultraviolet ray of (a). Then, the obtained coating film was annealed with warm air at 120 ℃ for 1 minute, thereby forming a 2 nd liquid crystal layer (C5).
(production of laminate)
The surface side of the 1 st liquid crystal layer (A1) formed on the produced long 1 st organic substrate and the surface side of the 2 nd liquid crystal layer (C5) formed on the produced long 2 nd organic substrate were subjected to 1 treatment using a corona treatment apparatus under conditions of 0.3kW output and 7.6 m/min treatment speed.
Next, the ultraviolet curable adhesive composition 1 was applied to the surface side of the 1 st liquid crystal layer (A1), and the surface side of the 2 nd liquid crystal layer (C5) formed on the 2 nd organic substrate was bonded so that the longitudinal direction of the film of the 1 st liquid crystal layer (A1) was parallel to the longitudinal direction of the film of the 2 nd liquid crystal layer (C5).
Next, the obtained laminate was irradiated with a high-pressure mercury lamp at an irradiation dose of 600mJ/cm 2 Ultraviolet rays (wavelength 365 nm) cure the adhesive layer. Thus, a laminate (a-C5) was obtained in which the 1 st organic base material, the 1 st liquid crystal layer (A1), the 2 nd liquid crystal layer (C5), and the 2 nd organic base material were laminated in this order.
Comparative example 1 >
A laminate was produced in the same manner as in example 1 except that the composition (C1) for forming a 2 nd liquid crystal layer in example 1 was changed to the composition (C6) for forming a 2 nd liquid crystal layer.
Comparative example 2 >
A laminate was produced in the same manner as in example 7 except that the 2 nd liquid crystal layer was produced as follows.
(formation of liquid Crystal layer 2)
A composition layer was formed by applying a 2 nd liquid crystal layer-forming composition (C7) containing a rod-like liquid crystal compound having the following composition to the cellulose acylate film 1 produced in example 1 using a die coater. Then, the composition was heated with warm air at 40℃for 60 seconds for drying the solvent and orientation curing of the liquid crystal compound.
Next, ultraviolet irradiation (300 mJ/cm) was performed at 40℃with an oxygen concentration of 100ppm under nitrogen purging 2 ) The alignment of the liquid crystal compound was fixed to form a retardation layer, thereby forming a 2 nd liquid crystal layer (C7).
Rod-like liquid crystal compound (L-1)
[ chemical formula 22]
Rod-like liquid crystal compound (L-2)
[ chemical formula 23]
Rod-shaped liquid crystal compound (L-3)
[ chemical formula 24]
Polymerizable monomer (L-4)
[ chemical formula 25]
Fluorine-based polymer (M-5) (the numerical value in each repeating unit represents the content (mass%) with respect to the total repeating units, and the weight-average molecular weight was 12500.)
[ chemical formula 26]
Fluorine-based polymer (M-6) (numerical values in each repeating unit represent content (mass%) with respect to the total repeating units, and the weight-average molecular weight is 12800.)
[ chemical formula 27]
Onium salt Compound S01
[ chemical formula 28]
Polymer M-4 (numerical value in each repeating unit represents content (mass%) with respect to the total repeating units) and having a weight-average molecular weight of 57000
[ chemical formula 29]
< evaluation method >)
(elastic modulus of Polymer)
Polymers M-1 to M-4 were dissolved in methyl ethyl ketone at a concentration of 40 mass%, and a polymer film was spin-coated on a glass substrate to a thickness of 20. Mu.m. The elastic modulus of the obtained polymer film was measured using a nanoindenter TI-950 (using a 1 μm spherical indenter, with an indentation load of 5 mN) manufactured by HYSITRON corporation.
(orientation of the 2 nd liquid Crystal layer)
From the above film in which the 2 nd liquid crystal layer was formed on the 2 nd organic substrate, a square film having a side length of 40mm was cut out. The obtained sample was observed with a polarized light microscope (using a 10-fold objective lens) under crossed nicols, and the liquid crystal alignment was evaluated based on the following criteria. The smaller the light leakage, the more excellent the liquid crystal alignment property.
A: no light leakage was observed in the field of view.
B: light leakage in the field of view is less.
C: light leakage exists in the observation field.
(measurement of Peel force P1 and Peel force P2)
The surface side of the 1 st liquid crystal layer formed on the 1 st organic substrate produced as described above was subjected to 1 treatment with a corona treatment apparatus under conditions of an output of 0.3kW and a treatment speed of 7.6 m/min.
Next, the ultraviolet curable adhesive composition 1 was applied to the surface side of the 1 st liquid crystal layer and bonded to the polarizer. The obtained laminate was irradiated with a high-pressure mercury lamp at an irradiation dose of 600mJ/cm 2 Ultraviolet rays (wavelength 365 nm) cure the adhesive layer.
Next, an adhesive layer was attached to the opposite surface of the polarizer to the surface to which the 1 st liquid crystal layer was attached. A test piece having a width of 25 mm. Times.150 mm in length was cut from the laminate having the adhesive layer formed thereon, and the adhesive layer side of the test piece was bonded to a glass plate. On the 1 st organic substrate side surface of the test piece, a release tape (width 25 mm. Times. Length about 180 mm) was attached to one side of the test piece having a width of 25 mm. The peel force P1 was measured by a tensile tester holding one end of the tape for peeling and performing a peeling test at a crosshead speed of 5 m/min and a peeling angle of 180 ° in an atmosphere at a temperature of 25 ℃ and a relative humidity of 60%. The peeling force P1 is a peeling force at which the force becomes stable until the peeling of the 1 st organic substrate from the 1 st liquid crystal layer is completed after the 1 st organic substrate is lifted.
In examples 1 to 6 and comparative example 1, 180 ° peel test of the 2 nd organic substrate was performed in the same procedure as described above except that a laminate (2 nd film) including the 2 nd organic substrate and the laminate (B1-C1) formed on the 2 nd organic substrate was used instead of the laminate (1 st film) including the 1 st organic substrate and the 1 st liquid crystal layer formed on the 1 st organic substrate used in the above, and the peel force P2 was measured.
In example 7 and comparative example 2, 180 ° peel test of the 2 nd organic substrate was performed in the same procedure as described above except that a laminate including the 2 nd organic substrate and the 2 nd liquid crystal layer formed on the 2 nd organic substrate was used instead of the laminate including the 1 st organic substrate and the 1 st liquid crystal layer formed on the 1 st organic substrate used in the above, and peel force P2 was measured.
(peelability of the 1 st organic substrate)
Test pieces having a width of about 1000mm by a length of about 500mm were cut from the laminate obtained in the examples. The end of the 1 st organic substrate was grasped by a stripper, and the peeling test was performed at a grasping movement speed of 10 m/min under an atmosphere having a relative humidity of 60% at a temperature of 23 ℃.
In addition, when the 1 st organic substrate is peeled off, peeling occurs between the 1 st organic substrate and the layer adjacent to the 1 st organic substrate or between the 2 nd organic substrate and the layer adjacent to the 2 nd organic substrate, and the larger the area that can be peeled off between the 1 st organic substrate and the layer adjacent to the 1 st organic substrate, the more excellent the peelability of the 1 st organic substrate.
A: the area of the peeling between the 1 st organic substrate and the layer adjacent to the 1 st organic substrate is 90% or more, and the area of the peeling between the 2 nd organic substrate and the layer adjacent to the 2 nd organic substrate is less than 10%.
B: the area of the peeling between the 1 st organic substrate and the layer adjacent to the 1 st organic substrate is 70% or more and less than 90%, and the area of the peeling between the 2 nd organic substrate and the layer adjacent to the 2 nd organic substrate is 10% or more and less than 30%.
C: the area of the peeling between the 1 st organic substrate and the layer adjacent to the 1 st organic substrate is less than 70%, and the area of the peeling between the 2 nd organic substrate and the layer adjacent to the 2 nd organic substrate is less than 30%.
(peelability of the 2 nd organic substrate)
The remaining laminate and polarizer obtained by peeling the 1 st organic substrate from the laminate in the above (peelability of the 1 st organic substrate) were bonded using the ultraviolet curable adhesive composition 1 so that the 1 st liquid crystal layer (the surface from which the 1 st organic substrate was peeled) became a bonding surface. The resulting laminate with polarizer was irradiated with an irradiation dose of 600mJ/cm using a high-pressure mercury lamp 2 Ultraviolet rays (wavelength 365 nm) cure the adhesive layer. Thus, an evaluation sample was prepared.
From the evaluation sample obtained above, the 2 nd organic substrate was gripped by a stripper and subjected to a peeling test at a gripping movement speed of 10 m/min under an atmosphere having a temperature of 23 ℃ and a relative humidity of 60%, and the evaluation was performed as follows.
A: can be peeled off without adhesion
B: can be adhered but can be peeled off
C: can not be peeled off
As shown in the above table, the laminate of the present invention exhibits desired effects.
Among these, it was confirmed by comparison of example 3 with other examples that the alignment property of the 2 nd liquid crystal layer and the peelability of the 1 st organic substrate were more excellent when the unevenness was 100 or less.
Further, it was confirmed by comparing example 3 and example 5 with other examples that the 1 st organic substrate was more excellent in peelability when P1/P2 was not more than 0.80.
Further, it was confirmed by comparison of example 4 with other examples that the peeling property of the 2 nd organic substrate was more excellent when the unevenness was 5.0 or more.
Further, it was confirmed by comparing examples 5 to 6 with other examples that the 1 st organic substrate and the 2 nd organic substrate were more excellent in peelability when the elastic modulus of the polymer was 0.04 to 0.15 GPa.
Symbol description
10-laminated body, 12-1 st organic base material, 14-1 st liquid crystal layer, 16-2 nd liquid crystal layer, 18-2 nd base material and 20-bonded object.
Claims (12)
1. A laminate comprising, in order, a 1 st organic substrate, a 1 st liquid crystal layer, a 2 nd liquid crystal layer, and a 2 nd organic substrate,
the peel force P1 between the 1 st organic substrate and the 1 st liquid crystal layer and the peel force P2 between the 2 nd organic substrate and the 2 nd liquid crystal layer satisfy the relationship of formula (A),
Formula (A) P1 < P2
The 2 nd liquid crystal layer comprises a polymer,
the unevenness obtained by the following unevenness calculating method was 3.0 or more,
the method for calculating the non-uniformity comprises the following steps: when measuring the secondary ion intensity from the polymer in the 2 nd liquid crystal layer by time-of-flight secondary ion mass spectrometry while irradiating an ion beam from the 2 nd organic substrate side surface of the 2 nd liquid crystal layer to the 1 st liquid crystal layer side surface, when the region from the depth position D20 to the depth position D50 is set to the 1 st liquid crystal layer side surface of the 2 nd liquid crystal layer, the maximum value I of the secondary ion intensity from the polymer in the surface region is set to the depth position D20, the depth position corresponding to 20% of the total thickness of the 2 nd liquid crystal layer is set to the depth position D50, the region from the 2 nd organic substrate side surface of the 2 nd liquid crystal layer to the depth position D20 is set to the surface region, and the region from the depth position D20 to the depth position D50 is set to the inner region A1 From the inner regionAverage value I of secondary ionic strength of polymer A2 The ratio is set to be non-uniformity.
2. The laminate according to claim 1, wherein,
the unevenness is 100 or less.
3. The laminate according to claim 1 or 2, wherein,
the peel force P1 and the peel force P2 satisfy the relationship of the formula (B),
the P1/P2 in the formula (B) is less than or equal to 0.80.
4. The laminate according to claim 1 or 2, wherein,
the 2 nd liquid crystal layer is in direct contact with the 2 nd organic substrate.
5. The laminate according to claim 1 or 2, wherein,
an adhesive layer or an adhesive layer is provided between the 1 st liquid crystal layer and the 2 nd liquid crystal layer.
6. The laminate according to claim 1 or 2, wherein,
a 3 rd liquid crystal layer is provided between the 1 st liquid crystal layer and the 2 nd liquid crystal layer,
the 2 nd liquid crystal layer is in direct contact with the 3 rd liquid crystal layer.
7. The laminate according to claim 1 or 2, wherein,
the elastic modulus of the polymer is 0.01-0.30 GPa.
8. The laminate according to claim 1 or 2, wherein,
the polymer contains a repeating unit represented by the following formula (1),
in the formula (1), R 1 Represents a hydrogen atom or a methyl group,
L 1 represents a single bond or is selected from the group consisting of-O-, -CO-, -NR 3 -a 2-valent aliphatic group which may have a substituent, a 2-valent aromatic group which may have a substituent, and a 2-valent linking group of a group consisting of combinations thereof, R 3 Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R 2 represents an alkyl group having 1 to 20 carbon atoms, wherein-CH constituting the alkyl group is the case with an alkyl group having 2 to 20 carbon atoms 2 More than 1 of them may also be substituted by-COO-or-CO-.
9. The laminate according to claim 8, wherein,
the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2),
in the formula (2), R 4 Represents a hydrogen atom or a methyl group.
10. An optical film obtained by peeling the 1 st organic substrate and the 2 nd organic substrate from the laminate according to any one of claims 1 to 9.
11. A polarizing plate having the optical film of claim 10.
12. An image display device having the polarizing plate according to claim 11.
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