阅读说明：本技术 层叠体、液晶显示装置、有机电致发光装置 (Laminate, liquid crystal display device, and organic electroluminescent device ) 是由 守田正人 柴田直也 于 2019-07-30 设计创作，主要内容包括：本发明的课题在于提供一种热耐久性优异且具有相位差层的层叠体、液晶显示装置及有机电致发光装置。本发明的层叠体为具有2个基板及配置于2个基板之间的偏振片的层叠体,其中,偏振片具有起偏器及相位差层,相位差层为使用包含逆波长分散性液晶化合物的组合物而形成的层,2个基板中的一个为Na-2O的含量为5质量％以下的玻璃基材,2个基板中的另一个为Na-2O的含量为5质量％以下的玻璃基材、透湿度为10～-～3g/m～2·day以下且厚度小于1μm的无机化合物膜、或透湿度为10～(-3)g/m～2·day以下的有机无机杂化膜。(The invention provides a laminated body with excellent thermal durability and a phase difference layer, a liquid crystal display device and an organic electroluminescent device. The laminate of the present invention is a laminate comprising 2 substrates and a polarizing plate disposed between the 2 substrates, wherein the polarizing plate comprises a polarizer and a retardation layer, the retardation layer is a layer formed using a composition comprising a reverse wavelength-dispersible liquid crystal compound, and one of the 2 substrates is Na 2 A glass base material having an O content of 5 mass% or less, and Na as the other of the 2 substrates 2 A glass substrate having an O content of 5 mass% or less and a moisture permeability of 10 ‑ 3 g/m 2 An inorganic compound film having a thickness of less than 1 μm and day or a moisture permeability of 10 ‑3 g/m 2 Organic-inorganic hybrid membranes below day.)

1. A laminate having 2 substrates and a polarizing plate disposed between the 2 substrates, wherein,

the polarizing plate has a polarizer and a phase difference layer,

the phase difference layer is formed by using a composition containing a reverse wavelength dispersion liquid crystal compound,

one of the 2 substrates is Na₂A glass base material having an O content of 5 mass% or less,

the other of the 2 substrates is Na₂A glass substrate having an O content of 5 mass% or less and a moisture permeability of 10^-3g/m²An inorganic compound film having a thickness of less than 1 μm and day or a moisture permeability of 10^-3g/m²Organic-inorganic hybrid membranes below day.

2. The laminate according to claim 1, wherein,

the polarizer comprises polyvinyl alcohol resin.

3. The laminate according to claim 1 or 2,

the reverse wavelength dispersion liquid crystal compound is a liquid crystal compound represented by a general formula (II),

L₁-G₁-D₁-Ar-D₂-G₂-L₂ (II)

in the general formula (II), D₁And D₂Each independently represents a single bond, -O-, -CO-O-, -C (═ S) O-, -CR¹R²-、-CR¹R²-CR³R⁴-、-O-CR¹R²-、-CR¹R²-O-CR³R⁴-、-CO-O-CR¹R²-、-O-CO-CR¹R²-、-CR¹R²-CR³R⁴-O-CO-、-CR¹R²-O-CO-CR³R⁴-、-CR¹R²-CO-O-CR³R⁴-、-NR¹-CR²R³-or-CO-NR¹-，

R¹、R²、R³And R⁴Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms,

G₁and G₂Each independently represents a 2-valent alicyclic hydrocarbon group or aromatic hydrocarbon group having 5 to 8 carbon atoms, and a methylene group contained in the alicyclic hydrocarbon group may be substituted by-O-, -S-, or-NH-,

L₁and L₂Each independently represents an organic group having a valence of 1, selected from the group consisting of L₁And L₂At least 1 of the groups represents a 1-valent group having a polymerizable group,

ar represents a 2-valent aromatic ring group represented by the general formula (II-1), the general formula (II-2), the general formula (II-3) or the general formula (II-4),

general formula (VII)

In the general formulae (II-1) to (II-4), Q₁represents-S-, -O-or-NR¹¹-，R¹¹Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y₁Z represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms₁、Z₂And Z₃Independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 1-valent carbon atom and 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group or-NR¹²R¹³or-SR¹²，Z₁And Z₂May be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring, R¹²And R¹³Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A₁And A₂Each independently is selected from the group consisting of-O-, -NR²¹A radical of the group consisting of-S-and-CO-, R²¹X represents a hydrogen atom or a substituent, X represents a non-metal atom of groups 14 to 16 to which a hydrogen atom or a substituent may be bonded, Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and having a substituent, or an aromatic hydrocarbon ring and an aromatic heterocyclic ringAt least one aromatic ring of (2-30 carbon atoms) in the group (A), wherein each of the aromatic rings Ax and Ay may have a substituent, Ax and Ay may be bonded to form a ring, and Q₂Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and represents a bonding position.

4. The laminate according to any one of claims 1 to 3,

the thickness of the polarizer is less than 10 μm.

5. The laminate according to any one of claims 1 to 4,

re (450) which is an in-plane retardation value at a wavelength of 450nm of the retardation layer, Re (550) which is an in-plane retardation value at a wavelength of 550nm of the retardation layer, and Re (650) which is an in-plane retardation value at a wavelength of 650nm of the retardation layer satisfy the relationship Re (450) Re (550) Re (650).

6. The laminate according to any one of claims 1 to 5,

the phase difference layer is a positive A plate.

7. The laminate according to any one of claims 1 to 6,

the phase difference layer is a lambda/4 plate.

8. The laminate according to any one of claims 1 to 7, further comprising a polarizer protective film on at least one surface of the polarizer,

at least one of the polarizer protective films contains a thermoplastic norbornene-based resin.

9. A liquid crystal display device having the laminate according to any one of claims 1 to 8.

10. An organic electroluminescent device having the laminate according to any one of claims 1 to 8.

Technical Field

The present invention relates to a laminate, a liquid crystal display device, and an organic electroluminescent device.

Background

Conventionally, a polarizing plate having a retardation layer and a polarizer has been used for a liquid crystal display device, an organic electroluminescence device, and the like for optical compensation, reflection prevention, and the like.

In recent years, polarizing plates (so-called broadband polarizing plates) have been developed which can provide the same effect to white light, which is a composite wave in which light rays in the visible light region are mixed, in accordance with light rays of all wavelengths, and in particular, in accordance with the demand for reduction in thickness of devices to which the polarizing plates are applied, reduction in thickness of a retardation layer included in the polarizing plate is also required.

In response to the above-described demand, for example, patent documents 1 and 2 propose the use of a liquid crystal compound exhibiting reverse wavelength dispersion as a liquid crystal compound for forming a retardation layer.

Prior art documents

Patent document

Patent document 1: international publication No. 2014/010325

Patent document 2: japanese patent laid-open publication No. 2011-207765

Disclosure of Invention

Technical problem to be solved by the invention

However, it is known that: when a polarizing plate having a retardation layer formed using the liquid crystal compound having reverse wavelength dispersibility described in patent documents 1 and 2 is produced and the polarizing plate is sandwiched between glass from both sides according to a practical use method (for example, a circular polarizing plate for preventing reflection in an organic electroluminescence type smartphone) and exposed to a high temperature condition for a long time, red color unevenness occurs in the central portion in the plane of the laminate. The results of the analysis clearly show that: in the red tone region, the in-plane retardation (Re) greatly fluctuates, and the tone changes. Therefore, it is desired to develop a laminate having a polarizer and a retardation layer, in which a change in-plane retardation is suppressed even when exposed to high temperatures for a long time. Hereinafter, the case where the change in-plane retardation is suppressed when the laminate is exposed to high temperature is expressed as excellent heat resistance.

Accordingly, an object of the present invention is to provide a laminate having a retardation layer and excellent thermal durability.

Another object of the present invention is to provide a liquid crystal display device and an organic electroluminescence device.

Means for solving the technical problem

The present inventors have conducted extensive studies to solve the above problems, and have found that the above problems can be solved by the following configuration.

(1) A laminate having 2 substrates and a polarizing plate disposed between the 2 substrates, wherein,

the polarizing plate has a polarizer and a phase difference layer,

the retardation layer is a layer formed using a composition containing a reverse wavelength-dispersible liquid crystal compound,

one of the 2 substrates is Na₂A glass base material having an O content of 5 mass% or less,

the other of the 2 substrates is Na₂A glass substrate having an O content of 5 mass% or less and a moisture permeability of 10^-3g/m²An inorganic compound film having a thickness of less than 1 μm and day or a moisture permeability of 10^-3g/m²Organic-inorganic hybrid membranes below day.

(2) The laminate according to (1), wherein,

the polarizer comprises polyvinyl alcohol resin.

(3) The laminate according to (1) or (2), wherein,

the reverse wavelength dispersion liquid crystal compound is a liquid crystal compound represented by the following general formula (II).

(4) The laminate according to any one of (1) to (3),

the thickness of the polarizer is less than 10 μm.

(5) The laminate according to any one of (1) to (4),

re (450) which is an in-plane retardation value at a wavelength of 450nm of the retardation layer, Re (550) which is an in-plane retardation value at a wavelength of 550nm of the retardation layer, and Re (650) which is a value of an in-plane retardation at a wavelength of 650nm of the retardation layer satisfy the relationship of Re (450) to Re (550) to Re (650).

(6) The laminate according to any one of (1) to (5),

the phase difference layer is a positive A plate.

(7) The laminate according to any one of (1) to (6),

the phase difference layer is a lambda/4 plate.

(8) The laminate according to any one of (1) to (7), further having a polarizer protective film on at least one surface of a polarizer,

at least one of the polarizer protective films contains a thermoplastic norbornene-type resin.

(9) A liquid crystal display device having the laminate of any one of (1) to (8).

(10) An organic electroluminescent device having the laminate of any one of (1) to (8).

Effects of the invention

According to the present invention, a laminate having a retardation layer and excellent thermal durability can be provided.

Further, the present invention can provide a liquid crystal display device and an organic electroluminescence device.

Drawings

Fig. 1A is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.

Fig. 1B is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.

Fig. 1C is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.

Fig. 1D is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.

Detailed Description

The laminate, the liquid crystal display device, and the organic electroluminescent device of the present invention will be described below.

In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values described before and after the term "to" are included as the lower limit value and the upper limit value.

The "orthogonal" and "parallel" angles are strict ranges of ± 10 ° in angle, and the "same" angle can be determined based on whether the difference is less than 5 °.

In the present specification, "visible light" means 380 to 780nm visible light. In the present specification, the measurement wavelength is 550nm when the measurement wavelength is not particularly described.

Next, terms used in the present specification will be described.

< Water content >

In the present specification, the "water content" refers to a mass obtained by converting the initial mass of a cut sample and the amount of change in the dry mass after drying at 120 ℃ for 2 hours, into a unit area.

< slow axis >

In the present specification, the "slow axis" refers to a direction in which the in-plane refractive index is the largest. The slow axis of the retardation layer refers to the slow axis of the entire retardation layer.

< Angle of inclination >

In the present specification, the "tilt angle" (also referred to as a tilt angle) refers to an angle formed by a tilted liquid crystal compound and a layer plane, and refers to a maximum angle among angles formed by a direction of a maximum refractive index in a refractive index ellipsoid of the liquid crystal compound and the layer plane. Therefore, in a rod-like liquid crystal compound having positive optical anisotropy, the tilt angle means the long axis direction of the rod-like liquid crystal compound, that is, the angle formed by the director direction and the layer plane. In the present invention, the "average tilt angle" refers to an average value of a tilt angle of an upper interface to a tilt angle of a lower interface of the retardation layer.

＜Re(λ)、Rth(λ)＞

The values of the in-plane retardation (Re (λ)) and the retardation in the thickness direction (Rth (λ)) are values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Opto Science, inc.).

Specifically, the average refractive index ((nx + ny + nz)/3) and the film thickness (d (. mu.m)) were input to Axoscan OPMF-1 to calculate

Slow axis direction (°)

Re(λ)＝R0(λ)

Rth (λ) ═ ((nx + ny)/2-nz) × d. R0 (. lamda.) is a numerical value calculated by Axoscan OPMF-1, but refers to Re (. lamda.).

Fig. 1A, 1B, 1C, and 1D are schematic cross-sectional views showing an example of the laminate of the present invention. Here, the laminate 10 shown in fig. 1A is a laminate having a layer structure of a glass substrate 17A, a polarizer protective film 11, a polyvinyl alcohol polarizer 12, a polarizer protective film 13, a positive a retardation layer 14, and a glass substrate 17B in this order.

The laminate 20 shown in fig. 1B has a layer structure including a glass substrate 17A, a polarizer protective film 11, a polyvinyl alcohol polarizer 12, a polarizer protective film 13, a positive a retardation layer 14, a positive C retardation layer 15, and a glass substrate 17B in this order.

The laminate 30 shown in fig. 1C has a layer structure including a glass substrate 17A, a polarizer protective film 11, a polyvinyl alcohol polarizer 12, a positive a retardation layer 14, a positive C retardation layer 15, and a glass substrate 17B in this order.

The laminate 40 shown in fig. 1D has a layer structure including a glass substrate 17A, a polarizer protective film 11, a polyvinyl alcohol polarizer 12, a polarizer protective film 13, a photo-alignment film 16, a positive a retardation layer 14, a positive C retardation layer 15, and a glass substrate 17B in this order.

As described above, the laminate of the present invention is a mode in which the polarizing plate including the polarizer and the retardation layer is sandwiched by 2 glass substrates corresponding to 2 substrates.

The polyvinyl alcohol polarizer is a polarizer containing a polyvinyl alcohol resin as a main component.

The positive a retardation layer is a retardation layer that is a positive a plate. The positive C retardation layer is a retardation layer that is a positive C plate.

Further, the glass substrate in FIGS. 1A to 1D is Na₂The content of O is 5 mass% or less.

In fig. 1A to 1D, the embodiment using 2 glass substrates has been described, but the embodiment is not limited thereto, and one of the 2 glass substrates in each figure may have a moisture permeability of 10^-3g/m²An inorganic compound film having a thickness of not more than 1 μm by day or a moisture permeability of 10^-3g/m²Organic-inorganic hybrid membranes below day.

In fig. 1A to 1D, an adhesive or a bonding agent is preferably used for bonding the film to the film, and the description of the adhesive or the bonding agent is omitted.

The respective members will be described in detail below.

< glass substrate >

In the laminate of the present invention, at least one of the 2 substrates is Na₂The content of O is 5 mass% or less (hereinafter, also referred to as "specific glass substrate"). More specifically, one of the 2 substrates sandwiching the polarizing plate is a specific glass substrate, and the other may be a specific glass substrate.

The above specific glass substrate is Na₂The content of O is 5 mass% or less based on the total mass of the glass substrate. In other words, the specific glass substrate is represented by mass% based on oxides, Na₂The content of O is 5 mass% or less.

In a specific glass substrate, Na₂The content of O may be 5 mass% or less, and is preferably 4 mass% or less, more preferably 2 mass% or less, and even more preferably 1 mass% or less, from the viewpoint of more excellent thermal durability of the laminate of the present invention (hereinafter, also simply referred to as "the viewpoint of more excellent effects of the present invention"). The lower limit is not particularly limited, and may be 0 mass%.

The specific glass substrate may contain Na in addition₂And other components except O. The specific glass substrate preferably comprises SiO₂. In a specific glass substrate, SiO₂The main component is preferred. The main component herein means a component having the largest content. And, SiO in the specific glass substrate₂Content (SiO relative to the total mass of the specific glass substrate)₂Content of (b) is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more in terms of mass% based on the oxide, from the viewpoint of further improving the effect of the present invention. The upper limit is not particularly limited, but is usually 95% by mass or less.

The specific glass substrate may contain Na in addition₂O and SiO₂Other components, for example, B₂O₃、Al₂O₃、CaO、MgO、K₂O and Fe₂O₃And oxides of atoms other than Na and Si.

In addition, in the specific glass substrate, Na is removed relative to the total mass of the specific glass substrate₂O₃And SiO₂The content of other components (oxides of other atoms) is not particularly limited, and is preferably 20% by mass or less from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, and may be 0% by mass or more.

I.e. Na in the specific glass substrate₂O and SiO₂The total content of (b) is preferably 80% by mass or more in terms of mass% based on oxides. The upper limit is not particularly limited, and may be 100 mass%.

In addition, the soda-lime glass, which is industrially mass-produced and has a cost advantage, has SiO as a main component₂(content: 65-75 mass%) and Na₂O (content: 10-20 mass%), CaO (content: 5-15 mass%), and more Na than the specific glass substrate₂O。

As Na₂The glass substrate having a smaller O content than soda lime glass includes borosilicate glass. As a representative composition of borosilicate glass, SiO is used in relation to the total mass of the glass₂68 to 82 mass% of B₂O₃The content of (A) is 7-14 mass%, Na₂The content of O is 3-5 mass%, K₂The content of O is 0 to 3 mass%. An example of the borosilicate glass is PIREX manufactured by Corning Incorporated co.

The thickness of the specific glass substrate is not particularly limited, but is preferably 1 μm or more, more preferably 1 to 2000 μm, and still more preferably 500 to 1500 μm.

< moisture permeability of 10^-3g/m²An inorganic compound film having a thickness of less than 1 μm and a day or less, and having a moisture permeability of 10^-3g/m²Organic-inorganic hybrid membranes under day >

In the laminate of the present invention, one of the 2 substrates sandwiching the polarizing plate may have a moisture permeability of 10^-3g/m²An inorganic compound film having a thickness of less than 1 μm and a moisture permeability of 10^-3g/m²Any of organic-inorganic hybrid films having a value of day or less (hereinafter, also simply referred to as "low moisture permeability substrate").

The low moisture permeability substrate has a moisture permeability (moisture permeability of an inorganic compound film having a thickness of less than 1 μm and moisture permeability of an organic-inorganic hybrid film) of 10^-3g/m²Day or less. Among them, from the viewpoint of durability of an organic electroluminescent device and a liquid crystal display device using a laminate, 10 is preferable^-4g/m²Day or less, more preferably 10^-5g/m²Day or less. The lower limit is not particularly limited, but is usually 10^-10g/m²Day or more.

The moisture permeability of the low moisture permeability substrate was measured as follows. The measurement was carried out using a water vapor transmission rate measuring apparatus (AQUATRAN 2 (registered trademark) manufactured by MOCON, inc.) under the conditions of a measurement temperature of 40 ℃ and a relative humidity of 90%.

The method for forming the inorganic compound film having a thickness of less than 1 μm can use any method as long as it is a method capable of forming the target thin layer. For example, a sputtering method, a vacuum evaporation method, an ion plating method, a plasma CVD (Chemical Vapor Deposition) method, and the like are applied, and specifically, the formation methods described in Japanese patent No. 3400324, Japanese patent laid-open Nos. 2002-322561, and 2002-361774 can be used.

The component contained In the inorganic compound film is not particularly limited as long as it can exhibit a low moisture permeability function, and for example, an oxide, nitride, or oxynitride of 1 or more elements selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, and Ta can be used. Among them, preferred is an oxide, nitride or oxynitride of an element selected from Si, Al, In, Sn, Zn and Ti, and preferred is an oxide, nitride or oxynitride of an element selected from Si, Al, Sn and Ti. These may contain other elements as auxiliary components.

Further, films composed of a reaction product of an aluminum compound and a phosphorus compound as described in Japanese patent laid-open Nos. 2016-040120 and 2016-155255 are also preferable.

Examples of the organic-inorganic hybrid film include a method of laminating a layer containing an organic material and an inorganic compound layer as described in U.S. Pat. No. 6413645, Japanese patent application laid-open No. 2015-226995, Japanese patent application laid-open No. 2013-202971, Japanese patent application laid-open No. 2003-335880, Japanese patent application laid-open No. 53-012953, and Japanese patent application laid-open No. 58-217344, and a layer in which an organic compound and an inorganic compound are hybridized as described in International publication No. 2011/011836, Japanese patent application laid-open No. 2013-248832, and Japanese patent application laid-open No. 3855004.

The thickness of the inorganic compound film is less than 1 μm, preferably 5 to 500nm, and more preferably 10 to 200 nm.

The thickness of the organic-inorganic hybrid film is preferably 0.1 to 10 μm, and more preferably 0.5 to 5.5 μm.

The low moisture permeability substrate is preferably transparent, and is preferably a so-called transparent substrate.

In the present specification, "transparent" means that the visible light transmittance is 60% or more, preferably 80% or more, and more preferably 90% or more. The upper limit is not particularly limited, but is usually less than 100%.

< retardation layer >

The laminated body has a phase difference layer. The retardation layer used in the present invention is a layer formed using a composition containing a reverse wavelength-dispersible liquid crystal compound.

Hereinafter, the components in the composition for forming the retardation layer will be described in detail, and then the method for producing the retardation layer and the properties thereof will be described in detail.

In the present specification, the reverse wavelength-dispersible liquid crystal compound means that when the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation layer produced using the reverse wavelength-dispersible liquid crystal compound is measured, the Re value becomes the same or greater as the measurement wavelength becomes larger, and as described later, the relationship of Re (450) ≦ Re (550) ≦ Re (650) is satisfied.

The liquid crystal compound is easily decomposed by water, and this problem tends to become remarkable when a reverse wavelength dispersion liquid crystal compound is used as the liquid crystal compound.

Specifically, the inventors have found that when a retardation layer produced using a reverse wavelength-dispersible liquid crystal compound is exposed to a high temperature condition, decomposition of the structure derived from the reverse wavelength-dispersible liquid crystal compound in the retardation layer rapidly occurs over a certain period of derivation, and the in-plane retardation value fluctuates more. This cause is presumed to be caused by the following phenomenon.

That is, as one method for making the reverse wavelength-dispersible liquid crystal compound reverse wavelength-dispersible, there is a case where it is made to have electron attractive property. It is presumed that the carbon atoms constituting the inverse wavelength-dispersible liquid crystal compound have increased positive polarization and are easily attacked by the affinity species (water).

Since the polarizing plate is sandwiched between predetermined substrates such as glass substrates, the change in Re under a high-temperature environment, which is the subject of the present invention, is thought to be caused by a slight amount of moisture originally contained in the polarizing plate (for example, polyvinyl alcohol-based resin for a polarizer) as a moisture supply source. The retardation layer formed by using the reverse wavelength-dispersible liquid crystal compound is subjected to the hydrolysis reaction, but the water content of the reaction factor is small because of the hydrophobic environment, and the supplied water content is considered to limit the rate of the hydrolysis reaction.

It is presumed that the moisture of the supply source diffuses in the in-plane direction before the hydrolysis reaction occurs in the end portions of the polarizing plate, the moisture diffuses from the end surfaces of the laminate to the outside of the laminate and is consumed, the amount of moisture supplied to the retardation layer is also reduced without the hydrolysis reaction, and the hydrolysis reaction occurs before the moisture of the supply source diffuses in the in-plane direction in the central portion of the polarizing plate, and the in-plane retardation value fluctuates.

When Na is used₂In the case of a glass substrate having a large O content, it is assumed that Na ions not eluted from the glass substrate promote the hydrolysis reaction of the reverse wavelength-dispersible liquid crystal compound.

In the present invention, it is presumed that the above-mentioned Na is used₂The glass substrate having an O content of less than a predetermined value suppresses the acceleration of the hydrolysis reaction, and as a result, a laminate exhibiting a desired effect is obtained.

(composition)

The composition for forming the retardation layer of the present invention (hereinafter, also simply referred to as "composition") contains a reverse wavelength dispersion liquid crystal compound.

The reverse wavelength-dispersive liquid crystal compound preferably has a polymerizable group.

The type of the polymerizable group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, styryl group, and allyl group.

The type of the reverse wavelength dispersive liquid crystal compound is not particularly limited, and can be classified into a rod type (rod-like liquid crystal compound) and a discotic type (discotic liquid crystal compound ) according to the shape thereof. Further, there are a low molecular type and a high molecular type, respectively. The polymer generally refers to a polymer having a polymerization degree of 100 or more (polymer physical/phase transition kinetics, edited by Otto-West university, page 2, Shibo bookshop, 1992). In the present invention, any liquid crystal compound can also be used.

Among them, rod-like liquid crystal compounds are preferably used. This is because there is an advantage that the retardation film formed can easily function as a positive a plate by uniformly (horizontally) aligning the rod-like liquid crystal compound.

As described above, the liquid crystal compound having reverse wavelength dispersibility is not particularly limited as long as it can form a retardation layer having reverse wavelength dispersibility, and examples thereof include a compound represented by the general formula (I) (particularly, compounds described in paragraphs [0034] to [0039 ]), which is described in jp 2008-297210 a, a compound represented by the general formula (1) (particularly, compounds described in paragraphs [0067] to [0073 ]), which is described in jp 2010-84032 a, and a liquid crystal compound represented by the general formula (II) which will be described later.

The reverse wavelength-dispersible liquid crystal compound is preferably a liquid crystal compound represented by the general formula (II) in view of more excellent reverse wavelength dispersibility.

L₁-G₁-D₁-Ar-D₂-G₂-L₂……(II)

In the general formula (II), D₁And D₂Each independently represents a single bond, -O-, -CO-O-, -C (═ S) O-, -CR¹R²-、-CR¹R²-CR³R⁴-、-O-CR¹R²-、-CR¹R²-O-CR³R⁴-、-CO-O-CR¹R²-、-O-CO-CR¹R²-、-CR¹R²-CR³R⁴-O-CO-、-CR¹R²-O-CO-CR³R⁴-、-CR¹R²-CO-O-CR³R⁴-、-NR¹-CR²R³-or-CO-NR¹-。

R¹、R²、R³And R⁴Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. In the presence of a plurality of R¹、R²、R³And R⁴In the case of each of (1), a plurality of R¹A plurality of R²A plurality of R³And a plurality of R⁴Each may be the same as or different from each other.

G₁And G₂Each independently represents a 2-valent alicyclic hydrocarbon group or aromatic hydrocarbon group having 5 to 8 carbon atoms, and a methylene group contained in the alicyclic hydrocarbon group may be substituted by-O-, -S-, or-NH-.

L₁And L₂Each independently represents an organic group having a valence of 1, selected from the group consisting of L₁And L₂At least 1 of the groups represents a 1-valent group having a polymerizable group,

ar represents a 2-valent aromatic ring group represented by the following general formula (II-1), general formula (II-2), general formula (II-3) or general formula (II-4). In the general formulae (II-1) to (II-4), a represents a bonding site.

[ chemical formula 1]

General formula (VII)

In the above general formulae (II-1) to (II-4), Q₁represents-S-, -O-or-NR¹¹-，

R¹¹Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

Y₁represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms (the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent),

Z₁、Z₂and Z₃Independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 1-valent carbon atom and 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group or-NR¹²R¹³or-SR¹²，

Z₁And Z₂May be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring, R¹²And R¹³Each independently represents a hydrogen atom orAn alkyl group having 1 to 6 carbon atoms,

A₁and A₂Each independently is selected from the group consisting of-O-, -NR²¹A radical of the group consisting of-S-and-CO-, R²¹Each represents a hydrogen atom or a substituent, and X represents a group 14 to 16 nonmetal atom to which a hydrogen atom or a substituent may be bonded (preferably, a ═ O, ═ S, ═ NR ', ═ C (R') R '(in which R' represents a substituent₂R (R represents alkyl). )),

ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and preferably includes an aromatic hydrocarbon ring group; an aromatic heterocyclic group; an alkyl group having 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; an alkenyl group having 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; an alkenyl group having 3 to 20 carbon atoms of at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring,

ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and a preferable mode of the organic group is the same as that of the organic group of Ax,

the aromatic rings in Ax and Ay may have a substituent, respectively, Ax and Ay may be bonded to each other to form a ring,

Q₂represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

Examples of the substituent that each of the above-mentioned groups may have include a halogen atom, an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a cyano group, an amino group, a nitro group, a nitroso group, a carboxyl group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, and combinations thereof.

With respect to the definition and preferred ranges of the respective substituents of the liquid crystal compound represented by the general formula (II), with respect to D₁、D₂、G₁、G₂、L₁、L₂、R¹、R²、R³、R⁴、Q₁、Y₁、Z₁And Z₂Reference can be made to D of the compound (A) described in Japanese patent laid-open publication No. 2012-021068¹、D²、G¹、G²、L¹、L²、R⁴、R⁵、R⁶、R⁷、X¹、Y¹、Q¹、Q²In connection with A₁、A₂And X, A of the compound represented by the general formula (I) described in Japanese patent laid-open No. 2008-107767 can be referred to₁、A₂Description of X for Ax, Ay, Q₂Reference may be made to Ax, Ay, Q of the compound represented by the general formula (I) described in International publication No. 2013/018526¹The description is related to. With respect to Z₃Reference can be made to Q in relation to the compound (A) described in Japanese patent laid-open publication No. 2012-021068¹The description of (1).

In particular, as a composition consisting of L₁And L₂The organic groups represented by, each is preferably represented by-D₃-G₃-Sp-P₃The group shown.

D₃And D₁The meaning is the same.

G₃Represents a single bond, a 2-valent aromatic or heterocyclic group having 6 to 12 carbon atoms, or a 2-valent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a methylene group contained in the alicyclic hydrocarbon group may be replaced by-O-, -S-or-NR⁷-substituted, wherein R⁷Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Sp represents a single bond, represented by- (CH)₂)_n-、-(CH₂)_n-O-、-(CH₂-O-)_n-、-(CH₂CH₂-O-)_m、-O-(CH₂)_n-、-O-(CH₂)_n-O-、-O-(CH₂-O-)_n-、-O-(CH₂CH₂-O-)_m、-C(＝O)-O-(CH₂)_n-、-C(＝O)-O-(CH₂)_n-O-、-C(＝O)-O-(CH₂-O-)_n-、-C(＝O)-O-(CH₂CH₂-O-)_m、-C(＝O)-N(R⁸)-(CH₂)_n-、-C(＝O)-N(R⁸)-(CH₂)_n-O-、-C(＝O)-N(R⁸)-(CH₂-O-)_n-、-C(＝O)-N(R⁸)-(CH₂CH₂-O-)_mOr- (CH)₂)_n-O-(C＝O)-(CH₂)_n-C(＝O)-O-(CH₂)_n-a spacer group of the formula. Wherein n represents an integer of 2 to 12, m represents an integer of 2 to 6, and R⁸Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. and-CH in each of the above groups₂The hydrogen atom of-may be substituted by methyl.

P₃Represents a polymerizable group.

The polymerizable group is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.

Examples of the radical polymerizable group include known radical polymerizable groups, and an acryloyl group or a methacryloyl group is preferable. It is known that an acryloyl group is generally polymerized at a high rate, and is preferable from the viewpoint of improving productivity, but a methacryloyl group can be similarly used as a polymerizable group for a highly birefringent liquid crystal.

Examples of the cationically polymerizable group include known cationically polymerizable groups, and examples thereof include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. Among them, an alicyclic ether group or an ethyleneoxy group is preferable, and an epoxy group, an oxetanyl group or an ethyleneoxy group is more preferable.

Examples of particularly preferable polymerizable groups include the following.

[ chemical formula 2]

In the present specification, the "alkyl group" may be any of linear, branched and cyclic groups, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a1, 1-dimethylpropyl group, a n-hexyl group, an isohexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.

Among these, from the viewpoint of more excellent effects of the present invention, it is preferable that Ar in the general formula (III) is a 2-valent aromatic ring group represented by the general formula (II-1) or Ar in the general formula (III) is a 2-valent aromatic ring group represented by the general formula (II-3), and D is₁And D₂At least one of which is a group other than-CO-O- (e.g., a single bond, -CR)¹R²-、-CR¹R²-CR³R⁴-、-O-CR¹R²-、-CR¹R²-O-CR³R⁴-、-CO-O-CR¹R²-、-O-CO-CR¹R²-、-CR¹R²-CR³R⁴-O-CO-、-CR¹R²-O-CO-CR³R⁴-、-CR¹R²-CO-O-CR³R⁴-、-NR¹-CR²R³-or-CO-NR¹-) in a controlled manner.

Preferred examples of the liquid crystal compound represented by the general formula (II) are shown below, but the liquid crystal compound is not limited thereto.

[ chemical formula 3]

[ chemical formula 4]

II-1-16

II-1-17

II-1-18

[ chemical formula 5]

In the above formula, "+" indicates a bonding position.

II-2-8

[ chemical formula 6]

II-2-9

[ chemical formula 7]

In the formulae II-2-8 and II-2-9, the group adjacent to the acryloyloxy group represents an allyl group (a group in which a methyl group is substituted with a vinyl group), and represents a mixture of positional isomers in which the methyl group is different in position.

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

II-3-26

II-3-27

II-3-28

II-3-29

[ chemical formula 11]

[ chemical formula 12]

II-3-55

[ chemical formula 13]

II-4-1

II-4-2

II-4-3

[ chemical formula 14]

[ chemical formula 15]

The content of the reverse wavelength-dispersible liquid crystal compound (for example, the liquid crystal compound represented by the general formula (II)) in the composition is not particularly limited, but is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 70 to 90% by mass, relative to the total solid content in the composition. The content is 70% by mass or more, and the reverse wavelength dispersibility is further excellent.

The solid content is other components excluding the solvent in the composition, and is calculated as a solid content even if the solid content is liquid.

The composition may contain a polymerizable rod-like compound in addition to the reverse wavelength-dispersible liquid crystal compound. The polymerizable rod-like compound does not consider the presence or absence of liquid crystallinity. By adding the polymerizable rod-like compound, the liquid crystal alignment property of the reverse wavelength dispersion liquid crystal compound can be controlled.

The polymerizable rod-like compound is preferably a compound having high compatibility with the reverse wavelength-dispersible liquid crystal compound because it is mixed with the reverse wavelength-dispersible liquid crystal compound and treated as a polymerizable composition.

The content of the polymerizable rodlike compound in the composition is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on the total mass of the reverse wavelength-dispersible liquid crystal compound.

The polymerizable rod-like compound is preferably a compound having a cyclohexane ring in which 1 hydrogen atom is partially substituted with a linear alkyl group.

Here, the "cyclohexane ring in which 1 hydrogen atom is substituted with a linear alkyl group" refers to, for example, a cyclohexane ring in which a hydrogen atom of a cyclohexane ring present on the molecular terminal side is substituted with 1 linear alkyl group in the case of having 2 cyclohexane rings, as shown in the following general formula (2).

The polymerizable rod-like compound includes, for example, a compound having a structure represented by the following general formula (2), and among them, a compound having a (meth) acryloyl group represented by the following general formula (3) is preferable from the viewpoint of further improving the effect of the present invention.

[ chemical formula 16]

In the general formula (2), a represents a bonding site.

And, in the above general formulae (2) and (3), R²Represents an alkyl group having 1 to 10 carbon atoms, n represents 1 or 2, W¹And W²Each independently represents an alkyl group, an alkoxy group or a halogen atomAnd, W¹And W²May be bonded to each other to form a ring structure which may have a substituent.

In the formula (3), Z represents-COO-or-OCO-, L represents an alkylene group having 1 to 6 carbon atoms, and R is³Represents a hydrogen atom or a methyl group.

Examples of such compounds include compounds represented by the following formulas A-1 to A-5. In addition, in the following formula A-3, R⁴Represents an ethyl or butyl group.

[ chemical formula 17]

The composition may contain other polymerizable liquid crystal compounds than the above-mentioned inverse wavelength dispersive liquid crystal compound.

The polymerizable group of the polymerizable liquid crystal compound is not particularly limited, and examples thereof include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

From the viewpoint of further improving the effect of the present invention, the other polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having 2 to 4 polymerizable groups, and more preferably a polymerizable liquid crystal compound having 2 polymerizable groups.

Examples of such polymerizable liquid crystal compounds include compounds represented by the formulae (M1), (M2) and (M3) described in paragraphs [0030] to [0033] of Japanese patent application laid-open No. 2014-077068, and more specifically, specific examples described in paragraphs [0046] to [0055] of Japanese patent application laid-open No. 2014-077068.

The polymerizable liquid crystal compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the other polymerizable liquid crystal compound when the composition contains the other polymerizable liquid crystal compound is not particularly limited, and is preferably 0 to 40 parts by mass, more preferably 0 to 10 parts by mass, based on 100 parts by mass of the total of the reverse wavelength dispersive liquid crystal compound and the other polymerizable liquid crystal compound.

From the viewpoint of further improving the effect of the present invention, the composition may contain a non-liquid crystalline polyfunctional polymerizable compound. This is presumably because, by increasing the crosslink density, the movement of the compound which is a catalyst of the hydrolysis reaction is suppressed, and as a result, the rate of the hydrolysis reaction is slowed, and during this time, moisture diffuses toward the end portions of the laminate.

On the other hand, a non-liquid crystal polyfunctional polymerizable compound is preferable because it may cause disorder of liquid crystal alignment. The acrylic equivalent is preferably 120 or less, more preferably 100 or less, and still more preferably 90 or less. Here, the acrylic equivalent means a value obtained by dividing the molecular weight by the number of acrylic functional groups.

Examples of the non-liquid crystal polyfunctional polymerizable compound include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1, 4-cyclohexane diacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 2, 3-cyclohexane tetramethylacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (for example, 1, 4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1, 4-divinylcyclohexanone), vinyl sulfones (e.g., divinylsulfone), acrylamides (e.g., methylenebisacrylamide), and methacrylamide.

Among them, the content of the non-liquid crystalline polyfunctional polymerizable compound is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.1 to 5% by mass (or preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 5% by mass), based on the total solid content in the composition, because the appearance of the retardation layer is diluted by increasing the content of the non-liquid crystalline polyfunctional polymerizable compound.

(polymerization initiator)

The composition may comprise a polymerization initiator.

The polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.

Examples of the photopolymerization initiator include an α -carbonyl compound (described in U.S. Pat. Nos. 2367661 and 2367670), an acyloin ether (described in U.S. Pat. No. 2448828), an α -hydrocarbon-substituted aromatic acyloin compound (described in U.S. Pat. No. 2722512), a polynuclear quinone compound (described in U.S. Pat. Nos. 3046127 and 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Pat. No. 3549367), an acridine and phenazine compound (described in Japanese patent publication No. 60-105667 and U.S. Pat. No. 4239850), an oxadiazole compound (described in U.S. Pat. No. 4212970), and an acylphosphine oxide compound (described in Japanese patent publication No. 63-040799, Japanese patent publication No. 5-029234, a naphthoquinone compound, a naphtho, Japanese patent laid-open Nos. H10-095788 and H10-029997).

From the viewpoint of further improving the effect of the present invention, the polymerization initiator is preferably an oxime-type polymerization initiator, and more preferably a polymerization initiator represented by the following general formula (III).

[ chemical formula 18]

In the general formula (III), X represents a hydrogen atom or a halogen atom, and Y represents a 1-valent organic group.

And, Ar³Represents a 2-valent aromatic group, L⁶R represents a C1-12 organic group having a valence of 2¹⁰Represents an alkyl group having 1 to 12 carbon atoms.

In the above general formula (III), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

In the above general formula (III), Ar is³The 2-valent aromatic group represented by (a) includes, for example, aromatic hydrocarbon rings having a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, and the like; and 2-valent groups of aromatic heterocycles such as furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothiazole ring.

And, in the above general formula (III), as L⁶Examples of the organic group having a valence of 2 and having 1 to 12 carbon atoms include linear or branched alkylene groups having 1 to 12 carbon atoms, and specifically include methylene, ethylene and propylene.

In the above general formula (III), R is¹⁰Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl and propyl.

In the general formula (III), examples of the 1-valent organic group represented by Y include compounds having a benzophenone skeleton ((C)₆H₅)₂CO) functional groups. Specifically, as in the groups represented by the following general formula (3a) and the following general formula (3b), a functional group having a benzophenone skeleton in which a terminal benzene ring is unsubstituted or monosubstituted is preferable.

[ chemical formula 19]

In the general formulae (3a) and (3b), a bonding position is a bonding position to a carbon atom of the carbonyl group in the general formula (III).

Examples of the oxime type polymerization initiator represented by the above general formula (III) include a compound represented by the following formula S-1 and a compound represented by the following formula S-2.

[ chemical formula 20]

The content of the polymerization initiator is not particularly limited, and is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the reverse wavelength-dispersible liquid crystal compound contained in the composition.

(alignment controlling agent)

The composition may comprise an orientation controlling agent. By using the alignment control agent, for example, the liquid crystal compound can be brought into a uniform alignment state in which the liquid crystal compound is aligned parallel to the surface of the layer.

As the orientation control agent, for example, a low molecular orientation control agent or a high molecular orientation control agent can be used. As the low-molecular orientation controlling agent, for example, the descriptions of paragraphs [0009] to [0083] of Japanese patent laid-open publication No. 2002-. Further, as the orientation controlling agent for the polymer, for example, the descriptions in paragraphs [0021] to [0057] of Japanese patent laid-open No. 2004-198511 and paragraphs [0121] to [0167] of Japanese patent laid-open No. 2006-106662 are cited in the present specification.

The content of the orientation controlling agent is not particularly limited, but the content of the orientation controlling agent is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total solid content in the composition.

(solvent)

The composition preferably contains a solvent from the viewpoint of workability for forming the retardation layer and the like. Examples of the solvent include water and an organic solvent.

Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (e.g., dioxane, tetrahydrofuran, and the like), aliphatic hydrocarbons (e.g., hexane, and the like), alicyclic hydrocarbons (e.g., cyclohexane, and the like), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene, and the like), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene, and the like), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate, and the like), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol, and the like), cellosolves (e.g., methyl cellosolve, and ethyl cellosolve), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, and the like), and amides (e.g., dimethylformamide, dimethylacetamide, and the like), these can be used alone in 1 kind, also can be used simultaneously in more than 2 kinds.

(other Components)

The composition may further contain other components than those described above, and for example, liquid crystal compounds other than those described above, leveling agents, surfactants, tilt angle control agents, alignment aids, plasticizers, and crosslinking agents can be cited.

(method for producing retardation layer)

The method for producing the retardation layer used in the present invention is not particularly limited, and known methods can be exemplified.

For example, the retardation layer can be produced by applying the composition to a predetermined substrate (for example, a support layer described later) to form a coating film, and subjecting the obtained coating film to a curing treatment (irradiation with an active energy ray (light irradiation treatment) and/or a heating treatment). Further, an alignment film described later may be used as necessary.

The coating of the composition can be carried out by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method).

In the method for producing the retardation layer, it is preferable that the coating film is subjected to an alignment treatment of the inverse wavelength-dispersible liquid crystal compound contained in the coating film before the coating film is subjected to a curing treatment. This makes it easy to form the obtained retardation layer into a positive a plate described later.

The orientation treatment can be performed by drying or heating at room temperature (e.g., 20 to 25 ℃). In the case where the liquid crystal phase formed in the alignment treatment is a thermotropic liquid crystal compound, it can be generally transferred in accordance with a change in temperature or pressure. In the case of a liquid crystal compound having lyotropic properties, the amount can be changed depending on the composition ratio such as the amount of the solvent.

For example, when the rod-like liquid crystal compound exhibits a smectic phase, one of temperature ranges in which the nematic phase is exhibited is generally higher than a temperature range in which the rod-like liquid crystal compound exhibits a smectic phase. Therefore, when the reverse wavelength-dispersible liquid crystal compound shows a smectic phase, the reverse wavelength-dispersible liquid crystal compound can be transferred from the nematic phase to the smectic phase by heating the reverse wavelength-dispersible liquid crystal compound to a temperature region where the nematic phase shows and then lowering the heating temperature to a temperature region where the reverse wavelength-dispersible liquid crystal compound shows a smectic phase. By this method, a positive a plate in which the reverse wavelength-dispersive liquid crystal compound is aligned with a high degree of order can be obtained.

When the orientation treatment is performed at a heating temperature, the heating time (heating aging time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, and still more preferably 10 seconds to 2 minutes.

The curing treatment (irradiation with an active energy ray (light irradiation treatment) and/or heating treatment) of the coating film described above can also be referred to as a fixing treatment for fixing the orientation of the reverse wavelength-dispersible liquid crystal compound.

Preferably, the immobilization treatment is performed by irradiation with an active energy ray (preferably, ultraviolet ray), and the liquid crystal is immobilized by polymerization of the inverse wavelength-dispersive liquid crystal compound.

(characteristics of retardation layer)

The retardation layer is formed using the composition.

The optical properties of the retardation layer are not particularly limited, but preferably function as a λ/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) in which an in-plane retardation Re (λ) at a specific wavelength λ nm satisfies Re (λ) ═ λ/4.

In the formula, it can be achieved at any wavelength in the visible light region (for example, 550nm), but it is preferable that the in-plane retardation Re (550) at a wavelength of 550nm satisfies the relationship of 110 nm. ltoreq. Re (550). ltoreq.160 nm, and more preferably, 110 nm. ltoreq. Re (550). ltoreq.150 nm.

Re (450) which is an in-plane retardation at a wavelength of 450nm of the retardation layer, Re (550) which is an in-plane retardation at a wavelength of 550nm of the retardation layer, and Re (650) which is an in-plane retardation at a wavelength of 650nm of the retardation layer satisfy the relationship of Re (450) to Re (550) to Re (650). That is, this relationship can be referred to as a relationship indicating the inverse wavelength dispersion property.

The in-plane retardation value at each wavelength was measured as described above.

The range of Re (550)/Re (450) is not particularly limited, but is preferably 1.05 to 1.25, more preferably 1.10 to 1.23. The range of Re (650)/Re (550) is not particularly limited, but is preferably 1.01 to 1.25, more preferably 1.01 to 1.10.

The retardation layer may be an a plate or a C plate, and is preferably a positive a plate.

The retardation layer may have a single-layer structure or a multilayer structure. In the case of a multilayer structure, it may be a stack of an a plate (e.g., a positive a plate) and a C plate (e.g., a positive C plate).

In the present specification, the positive a plate is defined as follows. In the positive a plate (positive a plate), the relationship of the formula (a1) is satisfied where nx is a refractive index in the slow axis direction (direction in which the in-plane refractive index is maximum) in the film plane, ny is a refractive index in the direction orthogonal to the in-plane slow axis, and nz is a refractive index in the thickness direction. Further, Rth of the positive a plate indicates a positive value.

Formula (A1) nx > ny ≈ nz

The term "substantially" as used herein includes not only the case where both are completely identical but also the case where both are substantially identical. Regarding "substantially the same", for example, the case where (ny-nz). times.d (where d is the thickness of the thin film) is-10 to 10nm, preferably-5 to 5nm is also included in "ny ≈ nz".

The positive a plate can be obtained by horizontally aligning a rod-like polymerizable liquid crystal compound such as the above-mentioned composition. For details of the method for producing the front a plate, for example, reference can be made to the descriptions of japanese patent application laid-open nos. 2008-225281 and 2008-026730.

In the present specification, the positive C plate is defined as follows. In the positive C plate (positive C plate), the relationship of expression (a2) is satisfied where nx is a refractive index in the slow axis direction (direction in which the in-plane refractive index is maximum) in the film plane, ny is a refractive index in the direction orthogonal to the in-plane slow axis, and nz is a refractive index in the thickness direction. In addition, Rth of the positive C plate represents a negative value.

Formula (A2) nx ≈ ny < nz

The term "substantially the same" as "substantially the same" is also included in the above description. The term "substantially the same", for example, the case where (nx-ny) × d (where d is the thickness of the thin film) is-10 to 10nm, preferably-5 to 5nm, is also included in "nx ≈ ny".

In the positive C plate, Re ≈ 0 according to the above definition.

The positive C plate can be obtained by vertically aligning a rod-like polymerizable liquid crystal compound. For details of the method for producing the front C plate, for example, reference can be made to the descriptions of japanese patent application laid-open nos. 2017-187732, 2016-053709, and 2015-200861.

The thickness of the retardation layer is not particularly limited, but is preferably 1 to 5 μm, more preferably 1 to 4 μm, and still more preferably 1 to 3 μm.

The relationship between the transmission axis of the polarizer and the slow axis of the retardation layer in the laminate is not particularly limited.

When the laminate is used for antireflection, the retardation layer is preferably a λ/4 plate, and the angle formed by the transmission axis of the polarizer and the slow axis of the retardation layer is preferably within a range of 45 ± 10 ° (35 to 55 °).

When the laminate is used for optical compensation of a tilt angle of IPS (In-Plane-Switching) liquid crystal, the retardation layer preferably has a multilayer structure of a positive A plate and a positive C plate having λ/4 plates, and the angle formed by the transmission axis of the polarizer and the slow axis of the retardation layer is In the range of 0 + -10 DEG (-10 DEG to 10 DEG) or 90 + -10 DEG (80 DEG to 100 DEG).

< polarizer >

The laminate of the present invention has a polarizer.

The polarizer (polarizing film) used is a so-called linear polarizer having a function of converting light into specific linearly polarized light. The polarizer is not particularly limited, and an absorption polarizer can be used.

The type of the polarizer is not particularly limited, and a known polarizer can be used, and examples thereof include polarizers made of polyvinyl alcohol resin.

The polyvinyl alcohol resin is a resin containing-CH₂Examples of the resin having a repeating unit of-CHOH-include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.

The polyvinyl alcohol resin is obtained by, for example, saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and copolymers with other monomers copolymerizable with vinyl acetate.

Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol resin is not particularly limited, but is preferably 85 to 100 mol%, more preferably 95.0 to 99.95 mol%. The degree of saponification can be determined in accordance with JIS K6726-.

The average polymerization degree of the polyvinyl alcohol resin is not particularly limited, but is preferably 100 to 10000, more preferably 1500 to 8000. The average degree of polymerization can be determined in accordance with JIS K6726-.

The content of the polyvinyl alcohol-based resin in the polarizer is not particularly limited, but it is preferable that the polarizer contains the polyvinyl alcohol-based resin as a main component. The main component is the content of polyvinyl alcohol resin is more than 50 mass% relative to the total mass of the polarizer. The content of the polyvinyl alcohol resin is preferably 90 mass% or more with respect to the total mass of the polarizer. The upper limit is not particularly limited, but is usually 99.9 mass% or less.

The polarizer preferably further comprises a dichromatic substance. Examples of the dichromatic substance include iodine and an organic dye (dichromatic organic dye). That is, the polarizer preferably contains polyvinyl alcohol as a main component and contains a dichromatic substance.

The method for producing the polarizer is not particularly limited, and a known method may be mentioned, and a method of adsorbing a dichromatic substance to a substrate containing polyvinyl alcohol and stretching the substrate may be mentioned.

Examples of the polarizer other than the polarizer containing the polyvinyl alcohol resin include a coating type polarizer prepared by coating a liquid crystal compound and a dichroic azo dye (for example, a dichroic azo dye for a light absorbing anisotropic film described in WO 2017-195833) as described in WO2017-195833 and jp 2017-083843 a.

The thickness of the polarizer is not particularly limited, but is preferably 1 to 20 μm, more preferably 1 to 15 μm, still more preferably 1 to 10 μm, and particularly preferably 1 to 5 μm. By reducing the thickness of the polarizer, not only can the thinning of the display device be realized, but also the water content can be further reduced, and the thermal durability can be further improved. The thickness of the polarizer is preferably less than 10 μm from the viewpoint of further improving the above properties.

< other layer >

The laminate of the present invention may have other components than the substrate, the retardation layer, and the polarizer.

The polarizing plate included in the laminate includes the retardation layer and a polarizer. Further, as described later, the polarizing plate may include a polarizer protective film.

The water content of the polarizing plate is not particularly limited, but is preferably 3g/m²Hereinafter, more preferably 2.3g/m²The concentration is more preferably 1.5g/m or less²Hereinafter, the most preferable is 0.8g/m²The following.

(support layer)

The stacked body may have a support layer for supporting the phase difference layer.

The support layer is preferably transparent, and specifically, the light transmittance is preferably 80% or more. As such a support, a polymer film is exemplified.

The thickness of the support layer is not particularly limited, but is preferably 5 to 80 μm, and more preferably 10 to 40 μm.

(alignment film)

The laminate may have an alignment film (alignment layer) having a function of defining the alignment direction of the liquid crystal compound.

The alignment film is a film (layer) provided on one surface of the retardation layer, and when the retardation layer includes the support layer, it is located between the support layer and the retardation layer.

In order to form a positive a plate as one embodiment of a retardation layer, a technique for bringing molecules of a liquid crystal compound into a desired alignment state is used, and for example, a technique for aligning a liquid crystal compound in a desired direction by an alignment film is generally used.

Examples of the alignment film include a rubbing treatment film of a layer containing an organic compound such as a polymer, a gradient deposition film of an inorganic compound, a film having a microgroove, and a film obtained by accumulating an LB (Langmuir-Blodgett) film formed of an organic compound such as ω -tricosanoic acid, dioctadecylmethylammonium chloride, and methyl stearate by the Langmuir-Blodgett method. Further, an alignment film which generates an alignment function by irradiation of light, and the like can be cited.

The alignment film is preferably formed by rubbing the surface of a layer containing an organic compound such as a polymer (polymer layer). The rubbing treatment is performed by rubbing the surface of the polymer layer several times in a certain direction (preferably, the longitudinal direction of the support) with paper or cloth. Examples of the polymer for forming the alignment film include polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraphs [0071] to [0095] of Japanese patent No. 3907735, and a polymer having a polymerizable group described in Japanese patent application laid-open No. 9-152509.

The thickness of the alignment film is not particularly limited, but is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

As the alignment film, a so-called photo alignment film (photo alignment layer) in which an alignment film is formed by irradiating a raw material having photo alignment properties with polarized light or unpolarized light is also preferably used. It is preferable that the optical alignment layer is given an alignment regulating force by a step of irradiating polarized light from a vertical direction or an oblique direction or a step of irradiating unpolarized light from an oblique direction.

By using the photo-alignment film, the liquid crystal compound can be aligned horizontally with excellent symmetry. Therefore, the positive a plate formed by using the photo-alignment film is particularly useful for optical compensation In a liquid crystal display device that does not require a pretilt angle for driving liquid crystal, such as an IPS (In-Plane-Switching) mode liquid crystal display device.

Examples of the photo-alignment material used for the photo-alignment film include, for example, Japanese patent laid-open Nos. 2006-285197, 2007-076839, 2007-138138, 2007-094071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, 3883848, 4151746, 2002-229039, 2002-265541, 2002-317013, and 2002-3113 maleimide and/or alkenyl-substituted nadiimide compounds having photo-alignment units, 4205195, The photocrosslinkable silane derivative described in Japanese patent No. 4205198, the photocrosslinkable polyimide, polyamide or ester described in Japanese patent publication No. 2003-520878, Japanese patent publication No. 2004-529220, Japanese patent publication No. 4162850, the photocrosslinkable polyimide, polyamide or ester described in Japanese patent publication No. 9-118717, Japanese patent publication No. 10-506420, Japanese patent publication No. 2003-505561, International publication No. 2010/150748, Japanese patent publication No. 2013-177561, and Japanese patent publication No. 2014-012823, the photodimerizable compound described in, in particular, the cinnamate compound, the chalcone compound, and the coumarin compound. Particularly preferred examples include azo compounds, photocrosslinkable polyimides, polyamides, esters, cinnamate compounds, and chalcone compounds.

The support layer and the alignment film may be provided independently as layers that perform their functions, or may serve as a single layer having both functions.

(polarizer protective film)

The laminate may also have a polarizer protective film. That is, at least one surface of the polarizer may be provided with a polarizer protective film. The polarizer protective film may be disposed only on one surface of the polarizer (on the surface opposite to the phase difference layer side), or may be disposed on both surfaces of the polarizer.

The structure of the polarizer protective film is not particularly limited, and may be a so-called transparent support or hard coat layer, or a laminate of a transparent support and a hard coat layer, for example.

As the hard coat layer, a known layer can be used, and for example, a layer obtained by polymerizing and curing a polyfunctional monomer may be used.

As the transparent support, a known transparent support can be used, and examples of materials for forming the transparent support include cellulose polymers typified by triacetylcellulose (hereinafter referred to as cellulose acylate), thermoplastic norbornene-based resins (ZEONEX manufactured by Zeon Corporation, ZEONOR, and ARTON manufactured by JSR Corporation), acrylic resins, polyester-based resins, and polystyrene-based resins. In order to suppress the total water content of the polarizing plate, a resin which is not easily hydrated, such as a thermoplastic norbornene-based resin and a polystyrene-based resin, is preferable, and a thermoplastic norbornene-based resin is more preferable.

The thickness of the polarizer protective film is not particularly limited, but is preferably 40 μm or less, more preferably 25 μm or less, from the viewpoint of enabling reduction in the thickness of the polarizing plate.

To ensure adhesion between the layers, the laminate may have an adhesive or bonding layer between the layers.

The laminate may have a transparent support between the layers.

The laminate may further have a retardation layer other than the retardation layer formed using the composition containing the liquid crystal compound represented by the above general formula (I).

The other phase difference layer may be an a plate or a C plate.

In addition, from the viewpoint of thinning of the member, the total thickness of the retardation layer and the other retardation layer formed using the composition containing the reverse wavelength-dispersible liquid crystal compound is preferably 100 μm or less, more preferably 40 μm or less, and further preferably 20 μm or less. From the viewpoint of manufacturing applicability, it is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more.

< method for producing laminate >

The method for producing the laminate is not particularly limited, and a known method can be used.

The following methods may be mentioned: first, a retardation layer formed on a predetermined support was bonded to a polarizer, and then the support was peeled off to produce a polarizing plate including the retardation layer and the polarizer, and the polarizing plate was sandwiched between 2 substrates to produce a laminate.

In addition, when the polarizing plate is manufactured, the retardation layer may be directly formed on the polarizer.

In the case of producing the polarizing plate, for example, it is preferable to include a step of continuously laminating a polarizer and each of the positive a plate and the positive C plate in a long state. The long polarizing plate is cut according to the size of the screen of the image display device used.

< use >)

The retardation layer in the laminate of the present invention is useful as an optical compensation film.

The optical compensation film can be suitably used for optical compensation of a Liquid Crystal Display (LCD) device, and can improve color tone change when viewed from an oblique direction and light leakage when displaying black. For example, an optical compensation film can be provided between a polarizer and a liquid crystal cell of an IPS liquid crystal display device. In particular, in the optical compensation of IPS liquid crystal, a large effect can be obtained by including a positive a plate and a positive C plate in the laminate.

For example, when the laminate of the present invention includes a positive a plate and a positive C plate, the polarizer may be laminated on the surface on the positive a plate side, or the polarizer may be laminated on the surface on the opposite side.

When the polarizer, the positive a plate, and the positive C plate are arranged in this order, the angle formed between the slow axis direction of the positive a plate and the absorption axis direction of the polarizing film is preferably in the range of 90 ° ± 10 °.

When the polarizer, the positive C plate, and the positive a plate are arranged in this order, the slow axis direction of the positive a plate is preferably parallel to the absorption axis direction of the polarizing film.

As the optical characteristics of the positive a plate and the positive C plate, the wavelength dispersion of Re or Rth is preferable to exhibit reverse dispersibility from the viewpoint of suppressing the change in color tone in particular.

The polarizing plate in the laminate of the present invention is useful as an antireflection plate.

More specifically, when the retardation layer in the polarizing plate is a λ/4 plate, the laminate can be suitably used as an antireflection plate. In particular, when the laminate includes the positive a plate and the positive C plate, the total Rth of the positive a plate and the positive C plate can be adjusted to be close to zero, and visibility in the oblique direction is improved.

When the laminate is used as an antireflection plate, the laminate can be suitably used for image display devices such as liquid crystal display devices (LCD), Plasma Display Panels (PDP), electroluminescent displays (ELD), and cathode ray tube display devices (CRT).

For example, the laminate of the present invention can be provided as an antireflection plate on the light extraction surface side of an organic EL display device. At this time, the external light is linearly polarized by the polarizer and then circularly polarized by the retardation plate. When the circularly polarized light is reflected by a metal electrode or the like of the organic EL display element, the circularly polarized light is inverted and when it passes through the retardation plate again, it becomes linearly polarized light inclined by 90 degrees from the incident time, and it reaches the polarizer and is absorbed. As a result, the influence of external light can be suppressed.

< liquid crystal display device, organic electroluminescent device >

The laminate can be preferably used for an organic electroluminescence device (preferably, an organic EL (electroluminescence) display device), a liquid crystal display device, and the like.

(liquid Crystal display device)

The liquid crystal display device of the present invention is an example of an image display device, and includes the laminate and the liquid crystal cell of the present invention described above.

In the present invention, among the polarizers provided on both sides of the liquid crystal cell, the polarizer in the laminate of the present invention is preferably used as the front polarizer, and more preferably the polarizers in the laminate of the present invention are used as the front and rear polarizers. The retardation layer included in the polarizing plate is preferably disposed on the liquid crystal cell side. In this case, the retardation layer can be suitably used as an optical compensation film.

In the laminate of the present invention, the substrate disposed on the liquid crystal layer side among the 2 substrates may function as a substrate disposed on both sides of the liquid crystal layer. For example, in the case where the substrates are specific glass substrates, the specific glass substrate disposed on the liquid crystal layer side among the 2 substrates in the laminate of the present invention can function as a glass substrate in a liquid crystal cell composed of a liquid crystal layer and the 2 glass substrates sandwiching the liquid crystal layer.

More specifically, as a liquid crystal display device including a laminate, a mode of an IPS liquid crystal display device for smart phones and tablet personal computers is cited, and as a configuration corresponding to the laminate, cover glass/(touch sensor)/(polarizer protective film)/polarizer/(polarizer protective film)/retardation layer/glass for liquid crystal cell is assumed. In this case, at least one of the cover glass and the liquid crystal cell glass is a specific glass base material corresponding to the substrate.

In addition, the component representations represented by () in the above structure may be absent.

Hereinafter, a liquid crystal cell constituting the liquid crystal display device will be described in detail.

The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.

In a TN mode liquid crystal cell, when no voltage is applied, rod-like liquid crystalline molecules are aligned substantially horizontally and are twisted by 60 to 120 degrees to be aligned. TN mode liquid crystal cells are most widely used as color TFT liquid crystal display devices and are described in many documents.

In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes (1) a narrow VA mode liquid crystal cell (described in japanese patent application laid-open No. 2-176625) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and are aligned substantially horizontally when a voltage is applied, and further includes (2) a liquid crystal cell (SID97, described in Digest of tech. papers 28 (1997)) 845) in which the VA mode is multi-domain (MVA mode) in order to enlarge a viewing angle, (3) a liquid crystal cell (n-ASM mode) in which the rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and are twisted in multi-domain alignment when a voltage is applied (described in proceedings 58 to 59 (1998)) of japan liquid crystal association), and (4) a liquid crystal cell (LCD International 98) in a surveyal mode. Further, any of a PVA (Patterned Vertical Alignment) type, a photo-Alignment type (Optical Alignment) and a PSA (Polymer-stabilized Alignment) type may be used. The details of these modes are described in detail in Japanese patent laid-open No. 2006-215326 and Japanese Table 2008-538819.

In the IPS mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially parallel to a substrate, and the liquid crystalline molecules respond in-plane by applying a parallel electric field to the substrate surface. The IPS mode displays black in a state where no electric field is applied, and absorption axes of a pair of upper and lower polarizing plates are orthogonal to each other. Jp-a-10-054982, jp-a-11-202323, jp-a-9-292522, jp-a-11-133408, jp-a-11-305217 and jp-a-10-307291 disclose methods for reducing light leakage during black display in an oblique direction by using an optical compensation sheet (optical compensation film) to improve the viewing angle.

(organic EL display device)

As an example of the organic EL display device of the present invention, a preferred embodiment includes a polarizing plate and an organic EL display panel of the present invention in this order from the viewing side. The retardation layer included in the polarizing plate is preferably disposed on the organic EL display panel side. In this case, the laminate of the present invention is used as an antireflection film.

In the laminate of the present invention, the substrate disposed on the organic EL display panel side among the 2 substrates can function as a sealing layer of the organic EL display panel. For example, in the case where the substrate is a specific glass substrate, the specific glass substrate disposed on the organic EL display panel side out of the 2 specific glass substrates in the laminate of the present invention can function as so-called sealing glass.

An organic EL display panel is a display panel including organic EL elements in which an organic light-emitting layer (organic electroluminescent layer) is interposed between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure can be adopted.

Among them, as an organic EL display device including a laminate, a mode of an organic EL display device for a smartphone or a tablet pc is cited, and as a configuration corresponding to the laminate, a cover glass/(touch sensor)/(polarizer protective film)/polarizer/(polarizer protective film)/phase difference layer/(touch sensor)/glass for organic EL sealing, a high barrier film, or an organic EL barrier film is assumed. In this case, at least one of the cover glass, the organic EL sealing glass, the barrier film, and the organic EL barrier film is a specific glass base material corresponding to the substrate.

In addition, a component represented by () that represents the above structure may not exist.

Examples

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited thereto.

< production of polarizer 1 with protective film >

The surface of the support of cellulose triacetate film TJ25 (manufactured by Fujifilm Corporation: thickness: 25 μm) was subjected to alkali saponification treatment. Specifically, the support was immersed in a 1.5-equivalent aqueous solution of sodium hydroxide at 55 ℃ for 2 minutes, and then washed in a water bath at room temperature, and further neutralized with 0.1-equivalent sulfuric acid at 30 ℃. After neutralization, the support was washed in a water bath at room temperature, and further dried with warm air at 100 ℃ to obtain a polarizer protective film.

A roll-shaped polyvinyl alcohol film having a thickness of 75 μm was stretched in an aqueous iodine solution in the MD (Machine Direction) Direction and dried to obtain a polarizer 1 having a thickness of 14 μm.

The polarizer protective films were attached to both surfaces of the polarizer 1, and the polarizer 1 with the protective films was produced.

< production of polarizer 2 with protective film >

The thickness and the draw ratio of the polyvinyl alcohol film were adjusted in the same manner as in the polarizer 1 with a protective film described above, and drying was carried out to obtain a polarizer 2 having a thickness of 9 μm.

The polarizer protective films are attached to both surfaces of the polarizer 2, and the polarizer 2 with the protective films is manufactured.

< preparation of glass substrates 1 to 3 >

Glass EAGLE-XG manufactured by Ltd was obtained as alkali-free glass and used as glass substrate 1 (Na)₂The content of O: 0 mass%).

Glass PIREX (Na) made by ltd. was obtained as borosilicate glass by Corning Incorporated co₂The content of O: 4 mass%), and as the glass substrate 2.

As the glass substrate 3, general alkali-lime glass (Na) was prepared₂The content of O: 17 mass%).

The glass substrates 1 to 3 have a width of 70mm, a length of 140mm and a thickness of 1.1 mm.

In addition, here, in the thermal durability test, in order to grasp Na estimated to promote the hydrolysis reaction of the liquid crystal compound₂The amount of elution of O from the glass substrate was determined, and as a result of examining the change in the glass mass when HCl solution (concentration: 5 mass%) having alkali components preferentially eluted was brought into contact with the glass substrate at 95 ℃ for 24 hours, the amount of decrease in the glass substrate 3 mass was 4 times that of the glass substrate 2. From the results, Na was confirmed₂O capacity ofEasily eluted into the glass substrate 3.

< example 1 >

The following composition was charged into a stirring tank and stirred to prepare a cellulose acetate solution used as a concentrated cellulose acylate solution for the core layer.

Compound G

[ chemical formula 21]

To 90 parts by mass of the above-mentioned core layer cellulose acylate dope was added 10 parts by mass of the following matting agent solution to prepare a cellulose acetate solution to be used as an outer layer cellulose acylate dope.

After the core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered by a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dopes on both sides thereof were simultaneously cast from a casting port onto a 20 ℃ roll in 3 layers (belt casting machine). The film was peeled from the roll in a state where the solvent content was about 20 mass%, both ends of the film in the width direction were fixed by tenter clips, and the film was stretched at a stretch ratio of 1.1 times in the transverse direction and dried. Then, the obtained film was transferred between rolls of a heat treatment apparatus and further dried to produce an optical film having a thickness of 40 μm, which was used as the optical film of example 1. The optical film of example 1 had a core layer thickness of 36 μm and outer layers disposed on both sides of the core layer each had a thickness of 2 μm. The Re (550) of the obtained optical film 1 was 0 nm.

Next, referring to the description of example 3 of jp 2012-155308 a, a coating solution 1 for a photo-alignment film is prepared and applied to the optical film 1 using a wire bar. Then, the obtained optical film was dried with warm air at 60 ℃ for 60 seconds to produce a coating film 1 having a thickness of 300 nm.

Next, the following coating liquid A-1 for forming a front plate A was prepared.

[ chemical formula 22]

The coating film 1 thus produced was irradiated with ultraviolet rays using an ultra-high pressure mercury lamp under the atmosphere. At this time, a wire grid polarizer (ProFlux PPL02, manufactured by Moxtek) was disposed parallel to the surface of the photo-alignment film 1, and photo-alignment treatment was performed to obtain the photo-alignment film 1.

In this case, the illuminance of the ultraviolet ray is 10mJ/cm in the UV-A region (ultraviolet ray A wave, integrated wavelength of 380-320 nm)²。

Next, the coating liquid a-1 for forming a positive a plate was applied to the photoalignment film 1 using a bar coater. The obtained coating film was heat-aged at a film surface temperature of 100 ℃ for 20 seconds and cooled to 90 ℃, and then irradiated with 300mJ/cm under air using an air-cooled metal halide lamp (EYE GRAPHICS Co., Ltd.; manufactured by Ltd.)²The nematic alignment state was fixed by the ultraviolet ray of (2) to form the retardation layer 1 (positive a plate a-1), and an optical film with the retardation layer 1 was produced.

The thickness of the retardation layer 1 was 2.5. mu.m. With respect to the retardation layer 1, Re (550) was 145nm, Rth (550) was 73nm, Re (550)/Re (450) was 1.12, Re (650)/Re (550) was 1.01, the tilt angle of the optical axis was 0 °, and the specific liquid crystal compound was uniformly aligned.

An adhesive-attached film was produced as described in example 1 of Japanese patent application laid-open No. 2017-134414.

Next, the retardation layer 1 side of the optical film with retardation layer 1 was bonded to one surface of the polarizer 1 with protective film using a film with an adhesive. At this time, the angle formed by the absorption axis of the polarizer and the slow axis of the phase difference layer 1 was 45 °. Specifically, the adhesive of the film with the adhesive is bonded to one surface of the polarizer 1 with the protective film, the film of the film with the adhesive is peeled, and the retardation layer 1 of the optical film with the retardation layer 1 is further bonded to the adhesive.

Next, the obtained laminate was peeled off at the interface between the photo-alignment film 1 and the retardation layer 1, and the optical film with the photo-alignment film 1 was removed, thereby producing a polarizing plate.

Then, the obtained polarizing plate was cut into the same width and length as those of the glass substrate 1, thereby producing the polarizing plate 1. Next, the glass substrate 1 was sandwiched from both sides of the polarizing plate 1 by using a film with an adhesive, and a laminate 1 including the glass substrate 1, the polarizing plate, and the glass substrate 1 in this order was obtained.

< example 2 >

A laminate 2 was obtained in the same manner as in example 1, except that the coating liquid a-2 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

Further, instead of the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1 and the specific liquid crystal compound L-2 of the coating liquid A-1 for forming a positive A plate, a coating liquid A-2 for forming a positive A plate was prepared by using 100 parts by mass of the following specific liquid crystal compound L-6.

[ chemical formula 23]

< example 3 >

A laminate 3 was obtained in the same manner as in example 1, except that the coating liquid a-3 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate. Further, a coating liquid A-3 for forming a positive A plate was prepared by using 100 parts by mass of the following specific liquid crystal compound L-9 in place of the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1 and the specific liquid crystal compound L-2 of the coating liquid A-1 for forming a positive A plate.

L-9

[ chemical formula 24]

< example 4 >

A laminate 4 was obtained in the same manner as in example 1, except that the coating liquid a-6 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

The following coating liquid A-6 for positive A plate formation was prepared.

[ chemical formula 25]

< example 5 >

A laminate 5 was obtained in the same manner as in example 1, except that a coating liquid a-7 for forming a positive a plate, which will be described later, was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-7 for forming a positive A plate using a specific liquid crystal compound L-8 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 26]

< example 6 >

A laminate 6 was obtained in the same manner as in example 1, except that a laminate 6 including a glass substrate 1, a polarizing plate, and a glass substrate 2 in this order was obtained using the glass substrates 1 and 2 instead of using 2 glass substrates 1.

Further, a glass substrate 1 is disposed on the side of the polarizing plate close to the positive a plate, and a glass substrate 2 is disposed on the side of the polarizing plate away from the positive a plate.

< example 7 >

A laminate 7 was obtained in the same manner as in example 6, except that the coating liquid a-2 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< example 8 >

A laminate 8 was obtained in the same manner as in example 6, except that the coating liquid a-3 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< example 9 >

A laminate 9 was obtained in the same manner as in example 6, except that the coating liquid a-6 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< example 10 >

A laminate 10 was obtained in the same manner as in example 6, except that a coating liquid a-7 for forming a positive a plate, which will be described later, was used in place of the coating liquid a-1 for forming a positive a plate.

< example 11 >

A laminate 11 was obtained in the same manner as in example 6, except that the coating liquid a-4 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-4 for forming a positive A plate using a specific liquid crystal compound L-5 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 27]

< example 12 >

A laminate 12 was obtained in the same manner as in example 6, except that a coating liquid a-5 for forming a positive a plate, which will be described later, was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-5 for forming a positive A plate using a specific liquid crystal compound L-10 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 28]

< example 13 >

A laminate 13 was obtained in the same manner as in example 6, except that the coating liquid a-8 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-8 for forming a positive A plate using a specific liquid crystal compound L-11 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 29]

< example 14 >

A laminate 14 was obtained in the same manner as in example 6, except that the coating liquid a-9 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-9 for forming a positive A plate using a specific liquid crystal compound L-12 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 30]

< example 15 >

A laminate 15 was obtained in the same manner as in example 6, except that the coating liquid a-9 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

Further, a coating liquid A-10 for forming a positive A plate using a specific liquid crystal compound L-13 described below in place of the specific liquid crystal compound L-7 of the coating liquid A-6 for forming a positive A plate was prepared.

[ chemical formula 31]

< comparative example 1 >

A laminate 16 was obtained in the same manner as in example 1, except that a laminate 16 including the glass substrate 1, the polarizing plate, and the glass substrate 3 in this order was obtained using the glass substrates 1 and 3 instead of using 2 glass substrates 1.

Further, a glass substrate 1 is disposed on the side of the polarizing plate close to the positive a plate, and a glass substrate 3 is disposed on the side of the polarizing plate away from the positive a plate.

< comparative example 2 >

A laminate 17 was obtained in the same manner as in comparative example 1, except that the coating liquid a-2 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< comparative example 3 >

A laminate 18 was obtained in the same manner as in comparative example 1, except that the coating liquid a-3 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< comparative example 4 >

A laminate 19 was obtained in the same manner as in comparative example 1, except that the coating liquid a-6 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< comparative example 5 >

A laminate 20 was obtained in the same manner as in comparative example 1, except that the coating liquid a-7 for forming a positive a plate described later was used in place of the coating liquid a-1 for forming a positive a plate.

< example 16 >

Next, the retardation layer 1 side of the optical film with the retardation layer 1 was bonded to one surface of the polarizer 2 with a protective film using a film with an adhesive. At this time, the angle formed by the absorption axis of the polarizer and the slow axis of the phase difference layer 1 was 45 °. Specifically, the adhesive of the film with the adhesive is bonded to one surface of the polarizer 1 with the protective film, the film of the film with the adhesive is peeled, and the retardation layer 1 of the optical film with the retardation layer 1 is further bonded to the adhesive.

Next, the obtained laminate was peeled off at the interface between the photo-alignment film 1 and the retardation layer 1, and the optical film with the photo-alignment film 1 was removed, thereby producing a polarizing plate.

Then, the obtained polarizing plate was cut into the same width and length as those of the glass substrate 1, thereby producing a polarizing plate 21. Next, a laminate 21 including the glass substrate 1, the polarizing plate, and the glass substrate 2 in this order was obtained by sandwiching the glass substrate 1 and the glass substrate 2 from both sides of the polarizing plate 1 with an adhesive film.

Further, a glass substrate 1 is disposed on the side of the polarizing plate close to the positive a plate, and a glass substrate 2 is disposed on the side of the polarizing plate away from the positive a plate.

< Heat durability test >

The laminates 1 to 21 were evaluated for thermal durability of in-plane retardation (Re) at a wavelength of 550nm in the central portion of the laminate using AxoScan (OPMF-1, manufactured by Axometrics) according to the following criteria. The results are shown in table 1 below.

In addition, as for the thermal durability test, a test was performed in which the test was left at 85 ℃ for 336 hours. If the evaluation is "a" or more, it can be judged that the durability is good.

AA: the change of the Re value after the test relative to the initial Re value is less than 2 percent of the initial value

A: the change amount of the Re value after the test relative to the initial Re value is more than 2% and less than 7% of the initial value

B: the change of the Re value after the test from the initial Re value is 7% or more of the initial value

The results of the above evaluation tests are shown in table 1.

[ Table 1]

As shown in table 1, it was confirmed that: the laminate of the present invention can provide desired effects.

In addition, from the comparison between example 1 and example 6, Na was confirmed₂When the content of O is lower, more excellent effects can be obtained.

Further, from comparison between examples 6 to 10 and examples 11 to 15, it was confirmed that when Ar in the general formula (III) is a 2-valent aromatic ring group represented by the general formula (II-1) or Ar in the general formula (III) is a 2-valent aromatic ring group represented by the general formula (II-3), and D is₁And D₂When at least one of them is a group other than-CO-O-, more excellent effects can be obtained.

< example 17 to example 32 >

(preparation of Positive C plate film 1)

As the dummy support, a triacetyl cellulose film "Z-TAC" (manufactured by FUJIFILM Corporation) (which is set as the cellulose acylate film 2) was used.

After passing the cellulose acylate film 2 through a dielectric heating roller having a temperature of 60 ℃ and raising the surface temperature of the film to 40 ℃, it was passed through a bar coater at 14ml/m²The alkali solution having the composition shown below was applied to one surface of the film and heated to 110 ℃ and transferred for 10 seconds under a steam type far infrared heater manufactured by Noritake Company, Limited.

Then, in the same mannerUsing a bar coater, 3ml/m²The pure water is coated on the film.

Subsequently, water washing by a jet coater and dehydration by an air knife were repeated 3 times, and then the film was transferred to a drying zone at 70 ℃ for 10 seconds and dried, thereby producing an alkali saponification-treated cellulose acylate film 2.

The coating liquid 2 for forming an alignment film having the following composition was continuously applied to the alkali-saponified cellulose acylate film 2 using a wire bar of # 8. The obtained film was dried with 60 ℃ warm air for 60 seconds, and further dried with 100 ℃ warm air for 120 seconds to form an alignment film.

The coating liquid C-1 for forming a front C plate described later was applied to an alignment film, and the obtained coating film was aged at 60 ℃ for 60 seconds and then used at 70mW/cm in air²The gas-cooled metal halide lamp (EYE GRAPHICS Co., Ltd.) irradiated at 1000mJ/cm²The alignment state of the liquid crystal compound was fixed by the ultraviolet ray of (2), and the liquid crystal compound was vertically aligned to produce a positive C plate film 1. The Rth (550) of the obtained positive C plate 1 was-60 nm.

[ chemical formula 32]

[ chemical formula 33]

[ chemical formula 34]

(preparation of polarizing plate)

The positive C plate film 1 prepared above was bonded to the positive a plate side of the polarizing plates of examples 1 to 16 using a film with an adhesive, and the alignment film and the cellulose acylate film 2 were removed to obtain polarizing plates 22 to 37.

(production of organic EL display device)

GALAXY S5 manufactured by SAMSUNG company, which is a product of mounting an organic EL display panel (organic EL display element), was disassembled to peel off a touch panel with a circularly polarizing plate from an organic EL display device, and further, the circularly polarizing plate was peeled off from the touch panel, thereby separating the organic EL display element (with sealing glass), the touch panel, and the circularly polarizing plate. Next, the separated touch panel was bonded to the organic EL display element again, the polarizing plate produced above was bonded to the touch panel so that the front C-plate side became the panel side, and a cover glass was further bonded to produce an organic EL display device. As the cover glass and the sealing glass, the glass substrate 1 was used.

The obtained organic EL display device includes a laminate including a sealing glass (corresponding to a glass plate), a polarizing plate (any of polarizing plates 22 to 37), and a cover glass (corresponding to a glass plate).

Description of the symbols

10. 20, 30, 40-laminate, 11-polarizer protective film, 12-polyvinyl alcohol polarizer, 13-polarizer protective film, 14-positive a plate, 15-positive C plate, 16-photo-alignment film, 17A-glass substrate, 17B-glass substrate.