TWI512088B - Liquid crystal display device - Google Patents

Description

Liquid crystal display device

The present invention relates to a liquid crystal display device.

The liquid crystal display device is currently used in various household electrical appliances, measuring machines, automobile panels, word processors, electronic notebooks, printing machines, computers, televisions, and the like, which are head clocks and calculators. Typical examples of the liquid crystal display method include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and IPS (transverse electric field effect) type. , OCB (optical compensation birefringence) type, ECB (electrically controlled birefringence) type, VA (vertical alignment) type, CSH (color super vertical alignment) type, or FLC ferroelectric liquid crystal). Further, as the driving method, the conventional static driving to multiplex driving is generally used, and in the simple matrix method, an active matrix (AM) method using TFT (thin film transistor) or TFD (thin film diode) driving has recently become mainstream.

As a method of producing a liquid crystal display device, a photocuring thermosetting method and a dropping method using a type sealant are widely used. In the dropping method, first, a rectangular sealing pattern is formed on one of the two transparent substrates with electrodes by means of a dispenser or screen printing. Then, a small droplet of liquid crystal is applied to the entire surface of the transparent substrate in a state where the sealant is not cured, and immediately overlaps with the other transparent substrate, and the sealing portion is irradiated with ultraviolet rays to be pre-cured. Thereafter, the liquid crystal is annealed at the time of liquid crystal annealing, and is finally hardened to produce a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element can be manufactured with high efficiency.

In the dropping method, there is a step in which the uncured sealant is directly in contact with the liquid crystal material, so contamination of the liquid crystal material caused by the sealant component becomes a big problem. Further, residues such as unreacted polymerization initiators and hardeners contained in the sealant after curing, and ionic impurities are also problematic. In recent years, there has been a tendency for liquid crystal panels to use a liquid crystal having a lower driving voltage (low-voltage liquid crystal) in accordance with the low power consumption of mobile applications and the like. In particular, the low-voltage type liquid crystal has a large dielectric anisotropy, and thus it is easy to take in impurities, and it is easy to cause disorder of alignment or decrease in voltage retention ratio with time. That is, there is a problem that the unreacted polymerization initiator contained in the sealant, the residue such as the initiator after hardening, the ionic impurities such as chlorine, and the decane coupling agent are eluted into the liquid crystal material, causing disorder or voltage of alignment. The retention rate decreases over time.

In this case, it is proposed to increase the softening point of the epoxy resin contained in the sealant in order to suppress elution of the sealant component into the liquid crystal material, thereby avoiding liquid crystal material caused by contact of the liquid crystal material with the uncured sealant. The pollution is intended to reduce color unevenness (Patent Document 1).

As another method for avoiding elution of the sealant component, there is proposed a method in which the sealant is a composition which can be hardened by light or heat, and after the sealant is applied, it is temporarily pre-hardened by light to avoid the cause When the liquid crystal material is contaminated by contact, the two substrates are bonded together and then hardened by heat (Patent Document 2). Therefore, an acrylic modified epoxy resin obtained by reacting an epoxy resin with acrylic acid is used as a sealing agent.

In general, epoxy resins have a higher adhesion force, but have a higher tendency to contaminate liquid crystal materials, and it is expected that the above-mentioned acrylic acid modification can simultaneously reduce contamination of liquid crystal materials. On the other hand, however, the thermosetting property may be lowered by the modification of acrylic acid, and contamination of the liquid crystal material due to elution of the sealant component may be observed. Therefore, it has also been proposed to add a tertiary amine such as imidazole to the curing of the acrylic component, and to thermally cure the acrylic resin by interaction with a small amount of epoxy resin blended at the same time (Patent Document 3).

However, any proposal assumes a general liquid crystal material, focusing on the composition of the sealant, carefully drilling In order to avoid the above problems, the composition of the sealant has been tried to avoid the above problems. Therefore, when applied to each liquid crystal display element, most of the display characteristics are not necessarily exhibited, and in particular, the image sticking phenomenon of the liquid crystal display element is not sufficiently improved.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-23582

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-18022

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-116825

The present invention has been proposed in view of the interaction between the composition of the liquid crystal material which has not been sufficiently studied and the sealant, and proposes a combination of a liquid crystal composition and a sealant composition for improving the characteristics of a liquid crystal display element such as a residual image.

That is, the present invention provides a practical liquid crystal layer temperature range and a large dielectric anisotropy (Δε) by using a specific liquid crystal composition and a cured product of a specific curable resin composition as a sealant. ) absolute value, low viscosity, and appropriate refractive index anisotropy (Δn), and prevention of lowering of the voltage holding ratio (VHR) of the liquid crystal layer, and solving display defects such as whitening, misalignment, and residual image The problem of the liquid crystal display device.

In order to solve the above problems, the inventors of the present invention have made an effort to study the combination of the curable resin composition constituting the sealant and the structure of the liquid crystal material constituting the liquid crystal layer. As a result, it has been found that the structure using a specific liquid crystal material and the specific hardenability are used. The liquid crystal display device of the sealant of the cured product of the resin composition prevents the voltage holding ratio (VHR) of the liquid crystal layer from being lowered, and solves the problem of poor display such as whitening, misalignment, and residual image, thereby completing the present invention.

That is, the present invention provides a liquid crystal display device having a first substrate, a second substrate, a liquid crystal layer containing a liquid crystal composition sandwiched between the first substrate and the second substrate, and via an energy line or a sealant in which the first substrate and the second substrate are bonded together by a cured product of a heat-hardened curable resin composition, and the liquid crystal composition contains one or two or more compounds represented by the formula (I). By,

(wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ are independently represented by trans-1,4- Cyclohexyl or 1,4-phenylene, one or two -CH ₂ - of the trans-1,4-cyclohexylene group can also be substituted by -O- in such a manner that the oxygen atoms are not directly adjacent to each other. One or two hydrogen atoms in the phenylene group may be substituted by a fluorine atom, X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group. , n ³¹ and n ³² independently represent 0, 1 or 2, n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ may be the same or different when there are a plurality of cases, the above hardenability The resin composition is a compound containing at least one (meth)acrylic group and an epoxy group in one molecule.

The liquid crystal display device of the present invention can have a practical liquid crystal layer temperature range and a large dielectric anisotropy by using a specific liquid crystal composition and a sealant using a cured product of a specific curable resin composition (Δε). ) absolute value, low viscosity, and appropriate refractive index anisotropy (Δn), and prevention of a decrease in the voltage holding ratio (VHR) of the liquid crystal layer, thereby preventing whitening, uneven alignment, image sticking, etc. Shows the occurrence of bad.

1‧‧‧Substrate

2‧‧‧Sealant

3‧‧‧LCD

4‧‧‧Driver driver

5‧‧‧Wiring from each pixel electrode

6‧‧‧Protective layer

7‧‧‧pixel electrode or wiring

8‧‧‧Alignment film

1 is a plan view of a liquid crystal display device of the present invention.

Figure 2 is an enlarged view of a liquid crystal display device of the present invention.

1 is a plan view of a liquid crystal display device of the present invention. Details of the pixel electrode, the TFT, the wiring, and the like are omitted. The top view of Fig. 2 is a partial view showing a part of the above plan view. The wiring extending from each of the pixel electrodes is displayed below the encapsulant to reach the driving driver. Figure 2 is a cross-sectional view of the upper diagram of Figure 2. The sealant contacts the liquid crystal and the alignment film. Not all of the cases are shown in the figure, depending on the position of the sealant, the sealant or liquid crystal contacts the wiring or the protective layer.

(liquid crystal layer)

The liquid crystal layer in the liquid crystal display device of the present invention is composed of a liquid crystal composition containing one or two or more compounds represented by the formula (I).

(wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M ³¹ to M ³³ independently of each other represent trans-1,4-cyclohexylene or 1,4-phenylene, and one or two of -CH ₂ - of the trans-1,4-extended cyclohexyl group can also The oxygen atom is not directly adjacent to -O-, and one or two hydrogen atoms in the phenyl group may be substituted by a fluorine atom, and X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, Z ³¹ Represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group, n ³¹ and n ³² independently represent 0, 1 or 2, n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ are present in plural In the case of the case, the same or different).

In the general formula (I), when R ³¹ is a phenyl group (aromatic) in the ring structure to which it is bonded, a linear alkyl group having 1 to 5 carbon atoms and a linear carbon are preferable. An alkoxy group having an atomic number of 1 to 4 (or more) and an alkenyl group having 4 to 5 carbon atoms, and a ring structure in which R ^{31 is} bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear chain are preferable. An alkenyl group having 2 to 5 carbon atoms.

If it is considered that the chemical stability to heat or light is good, R ^{31 is} preferably an alkyl group. Further, in order to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{31 is} preferably an alkenyl group. Further, if the viscosity is small and the nematic phase-isotropic phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having a terminal which is not an unsaturated bond, and more preferably a methyl group. It is present as a terminal at the side of the alkenyl group. Further, if it is considered that the solubility at a low temperature is good, it is preferable to set R ³¹ as an alkoxy group as one of the solutions. Further, as another solution, it is preferred to use a plurality of R ^{31 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ is preferably used in combination, and a compound having an alkyl group or an alkenyl group having 3 and 5 carbon atoms as R ³¹ is preferably used in combination. It is preferred to use a compound having an alkyl group or an alkenyl group having 3, 4 and 5 carbon atoms as R ³¹ in combination.

M ³¹ ~ M ^{33 is} preferably

M ^{31 is} preferably Further preferably

M ^{32 is} preferably Better Further preferably

M ^{33 is} preferably Better Further preferably

X ³¹ and X ^{32 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

Z ^{31 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ =F, X ³² =F and Z ³¹ =F. Further, in another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = F. Further, in still another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = OCF3. Further, in still another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF3. Further, in still another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF3. n ^{31 is} preferably 1 or 2, and n ^{32 is} preferably 0 or 1, more preferably 0, and n ³¹ + n ^{32 is} preferably 1 or 2, and further preferably 2.

More specifically, the compound represented by the formula (I) is preferably a compound represented by the following formula (I-a) to formula (I-f).

(wherein R ³² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, X ³¹ to X ³⁸ represent a hydrogen atom or a fluorine atom independently of each other, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group).

In the general formula (Ia) to the formula (If), when R ³² is a phenyl group (aromatic) in the ring structure to which the bond is bonded, a linear alkyl group having 1 to 5 carbon atoms is preferred. a linear alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which R ^{32 is} bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear chain are preferable. An alkenyl group having 2 to 5 carbon atoms.

If it is considered that the chemical stability to heat or light is good, R ^{31 is} preferably an alkyl group. Further, in order to produce a liquid crystal display element having a small viscosity and a fast response speed, R ^{31 is} preferably an alkenyl group. Further, if the viscosity is small and the nematic phase-isotropic phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having a terminal which is not an unsaturated bond, and more preferably a methyl group. It is present as a terminal at the side of the alkenyl group. Further, if it is considered that the solubility at a low temperature is good, it is preferable to set R ³¹ as an alkoxy group as one of the solutions. Further, as another solution, it is preferred to use a plurality of R ^{31 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ³¹ is preferably used in combination, and a compound having an alkyl group or an alkenyl group having 3 and 5 carbon atoms as R ³¹ is preferably used in combination. It is preferred to use a compound having an alkyl group or an alkenyl group having 3, 4 and 5 carbon atoms as R ³¹ in combination.

X ³¹ and X ^{32 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

Z ^{31 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ³¹ , X ³² and Z ³¹ , in one embodiment, X ³¹ =F, X ³² =F and Z ³¹ =F. Further, in another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = F. Further, in still another embodiment, X ³¹ = F, X ³² = H, and Z ³¹ = OCF3. Further, in still another embodiment, X ³¹ = F, X ³² = F, and Z ³¹ = OCF3. Further, in still another embodiment, X ³¹ = H, X ³² = H, and Z ³¹ = OCF3.

n ^{31 is} preferably 1 or 2, and n ^{32 is} preferably 0 or 1, more preferably 0, and n ³¹ + n ^{32 is} preferably 1 or 2, and further preferably 2.

X ³³ and X ^{34 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

It is preferred that at least one of X ³⁵ and X ³⁶ is a fluorine atom, and both of them are effective when the fluorine atom is increased by Δ ε, but in the case of Tni, solubility at a low temperature or when a liquid crystal display element is formed The chemical stability is not good.

X ³⁷ and X ^{38 are} preferably at least one of hydrogen atoms, and preferably both of them are hydrogen atoms. When at least one of X ³⁷ and X ³⁸ is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, or chemical stability when a liquid crystal display element is formed.

The compound group represented by the formula (I) preferably contains one to eight kinds, more preferably one to five kinds, and the content thereof is preferably from 3 to 50% by mass, more preferably from 5 to 40% by mass.

The liquid crystal composition in the liquid crystal display device of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the general formula (II-a) to the general formula (II-f).

(wherein R ¹⁹ to R ³⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or fluorine. atom).

In the general formula (IIa) to the general formula (IIf), when R ¹⁹ to R ^{30 are} bonded to a phenyl group (aromatic), the linear carbon number is preferably 1 to 5 An alkyl group, a linear alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, and a ring structure in which R ¹⁹ to R ^{30 are} bonded is a ring Alkane, pyran and two In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear chain are preferable. An alkenyl group having 2 to 5 carbon atoms.

When it is considered that the chemical stability to heat or light is good, R ¹⁹ to R ^{30 are} preferably an alkyl group. Further, in order to produce a liquid crystal display element having a small viscosity and a fast response speed, R ¹⁹ to R ^{30 are} preferably an alkenyl group. Further, if the viscosity is small and the nematic phase-isotropic phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having a terminal which is not an unsaturated bond, and more preferably a methyl group. It is present as a terminal at the side of the alkenyl group. Further, if it is considered that the solubility at a low temperature is good, it is preferable to set R ¹⁹ to R ³⁰ as an alkoxy group as one of the solutions. Further, as another solution, it is preferred to use a plurality of types of R ¹⁹ to R ^{30 in combination} . For example, a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ¹⁹ to R ³⁰ is preferably used in combination, and a compound having a carbon number of 3 and 5 as R ¹⁹ to R ³⁰ is preferably used in combination. It is preferred to use a compound having a carbon number of 3, 4 and 5 as R ¹⁹ to R ³⁰ in combination.

R ¹⁹ to R ^{20 are} preferably an alkyl group or an alkoxy group, and preferably at least one is an alkoxy group. More preferably, R ¹⁹ is an alkyl group and R ²⁰ is an alkoxy group. Further, R ¹⁹ is preferably an alkyl group having 3 to 5 carbon atoms, and R ²⁰ is an alkoxy group having 1 to 2 carbon atoms.

R ²¹ to R ^{22 are} preferably an alkyl group or an alkenyl group, and preferably at least one is an alkenyl group. When both of them are alkenyl groups, they can be preferably used for accelerating the response speed, but it is not preferable in the case where the chemical stability of the liquid crystal display element is to be improved.

Preferably, at least one of R ²³ to R ²⁴ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. When the balance between the response speed and the Tni is good, at least one of R ²³ to R ²⁴ is preferably an alkenyl group, and if the balance between the response speed and the solubility at a low temperature is good, R ²³ ~ is preferable. At least one of R ²⁴ is an alkoxy group.

Preferably, at least one of R ²⁵ to R ²⁶ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. When the balance between the response speed and the Tni is good, at least one of R ²⁵ to R ²⁶ is preferably an alkenyl group, and if the balance between the response speed and the solubility at a low temperature is good, R ²⁵ ~ is preferable. At least one of R ²⁶ is an alkoxy group. More preferably, R ²⁵ is an alkenyl group and R ²⁶ is an alkyl group. Further, it is also preferred that R ²⁵ is an alkyl group and R ²⁶ is an alkoxy group.

Preferably, at least one of R ²⁷ to R ²⁸ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. When the balance between the response speed and the Tni is good, at least one of R ²⁷ to R ²⁸ is preferably an alkenyl group, and when the balance between the response speed and the solubility at a low temperature is good, R ²⁷ ~ is preferable. At least one of R ²⁸ is an alkoxy group. More preferably, R ²⁷ is an alkyl group or an alkenyl group, and R ²⁸ is an alkyl group. Further, it is also preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkoxy group. Further, it is particularly preferred that R ²⁷ is an alkyl group and R ²⁸ is an alkyl group.

X ^{21 is} preferably a fluorine atom.

Preferably, at least one of R ²⁹ to R ³⁰ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. When the balance between the response speed and the Thi is good, at least one of R ²⁹ to R ³⁰ is preferably an alkenyl group, and if the reliability is good, at least one of R ²⁹ to R ³⁰ is preferably an alkyl group. . More preferably, R ²⁹ is an alkyl group or an alkenyl group, and R ³⁰ is an alkyl group or an alkenyl group. Further, it is also preferred that R ²⁹ is an alkyl group and R ³⁰ is an alkenyl group. Further, it is also preferred that R ²⁹ is an alkyl group and R ³⁰ is an alkyl group.

The compound group represented by the formula (II-a) to the formula (II-f) preferably contains one to ten kinds, more preferably one to eight kinds, and the content thereof is preferably from 5 to 80% by mass. More preferably, it is 10 to 70% by mass, and particularly preferably 20 to 60% by mass.

The liquid crystal composition layer in the liquid crystal display device of the present invention may further contain one or more compounds selected from the group consisting of compounds represented by the general formulae (III-a) to (III-f).

(wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms, X ⁴¹ to X ⁴⁸ represent a hydrogen atom or a fluorine atom independently of each other, and Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group).

In the general formula (IIIa) to the general formula (IIIf), when R ⁴¹ is a phenyl (aromatic) ring structure, it is preferably a linear alkyl group having 1 to 5 carbon atoms. a linear alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which R ^{41 is} bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, and a linear chain are preferable. An alkenyl group having 2 to 5 carbon atoms.

If the importance of a good chemical stability of heat or light, then R ⁴¹ is preferably an alkyl group, and, if the viscosity produced less attention, response speed of the liquid crystal display element, then R ⁴¹ is preferably an alkenyl group. Further, if the viscosity is small and the nematic phase-isotropic phase transition temperature (Tni) is high and the response speed is further shortened, it is preferred to use an alkenyl group having a terminal which is not an unsaturated bond, and more preferably a methyl group. It is present as a terminal at the side of the alkenyl group. Further, if it is considered that the solubility at a low temperature is good, it is preferable to use R ⁴¹ as an alkoxy group as one of the solutions. Further, as another solution, it is preferred to use a plurality of R ^{41 in combination} . For example, it is preferred to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms as R ⁴¹ in combination, preferably a compound having a carbon number of 3 and 5 as R ⁴¹ , preferably a combined carbon. The number of atoms 3, 4 and 5 is a compound of R ⁴¹ .

X ⁴¹ and X ^{42 are} preferably at least one of fluorine atoms, and more preferably both of them are fluorine atoms.

Z ^{41 is} preferably a fluorine atom or a trifluoromethoxy group.

As a combination of X ⁴¹ , X ⁴² and Z ⁴¹ , in one embodiment, X ⁴¹ = F, X ⁴² = F and Z ⁴¹ = F. Further, in another embodiment, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = F. Further, in still another embodiment, X ⁴¹ = F, X ⁴² = H, and Z ⁴¹ = OCF3. Further, in still another embodiment, X ⁴¹ = F, X ⁴² = F, and Z ⁴¹ = OCF3. Further, in still another embodiment, X ⁴¹ = H, X ⁴² = H, and Z ⁴¹ = OCF3. It is preferred that at least one of X ⁴³ and X ⁴⁴ is a fluorine atom, and both of them have a large Δ ε of a fluorine atom, which is preferable, but conversely, it is owed when the solubility at a low temperature is improved. good.

Preferably, at least one of X ⁴⁵ and X ⁴⁶ is a hydrogen atom, and both of them are each a hydrogen atom. The use of a large amount of fluorine atoms is not preferable from the viewpoint of Tni, solubility at low temperatures, or chemical stability when formed into a liquid crystal display element.

Preferably, at least one of X ⁴⁷ and X ⁴⁸ is a hydrogen atom, and preferably both of them are hydrogen atoms. When at least one of X ⁴⁷ and X ⁴⁸ is a fluorine atom, it is not preferable from the viewpoints of Tni, solubility at low temperature, or chemical stability when formed into a liquid crystal display element.

The compound selected from the group consisting of the compound represented by the formula (III-a) to the formula (III-f) preferably contains one to ten kinds, more preferably one to eight kinds, and the content thereof is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

The liquid crystal composition of the liquid crystal composition layer in the liquid crystal display device of the present invention preferably has a Δ ε at 25 ° C of +1.5 or more. For the purpose of high-speed response, Δε at 25 ° C is preferably +1.5 to +4.0, more preferably +1.5 to +3.0. For the purpose of driving at a low voltage, Δε at 25 ° C is preferably +8.0 to +18.0, more preferably +10.0 to +15.0. Further, Δn at 25 ° C is preferably from 0.08 to 0.14, more preferably from 0.09 to 0.13. If it is described in detail, the Δn at 25 ° C is preferably 0.10 to 0.13 in the case of a relatively thin cell gap, and the Δn at 25 ° C is preferably 0.08 〜 in the case of a thicker cell gap. 0.10. The η at 20 ° C is preferably 5 to 45 mPa ‧ s, more preferably 5 to 25 mPa ‧ s, and particularly preferably 10 to 20 mPa ‧ s. Further, T _{ni is} preferably 60 ° C to 120 ° C, more preferably 70 ° C to 100 ° C, and particularly preferably 70 ° C to 85 ° C.

The liquid crystal composition in the liquid crystal display device of the present invention may contain, in addition to the above compounds, a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal or the like. However, the compound having a chlorine atom in the liquid crystal composition is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and preferably substantially not contained. The term "substantially does not contain" means that a compound which is not intended to contain a chlorine atom, such as a compound which is formed as an impurity at the time of production of the compound, is mixed into the liquid crystal composition.

In the liquid crystal display device of the liquid crystal display device of the present invention, one or two or more kinds of polymerizable compounds may be contained in order to produce a liquid crystal display element such as a PS mode, a lateral electric field type PSA mode or a lateral electric field type PSVA mode. Examples of the polymerizable compound which can be used include a photopolymerizable monomer which is polymerized by an energy ray such as light, and examples of the structure include, for example, A polymerizable compound having a liquid crystal skeleton in which a plurality of six-membered rings are bonded, such as a biphenyl derivative or a terphenyl derivative. More specifically, a difunctional monomer represented by the formula (V) is preferred.

(wherein, X ⁵¹ and X ⁵² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH _{2 ) s} - (wherein, s represents an integer from 2 to 7, and the oxygen atom is set to be bonded to the aromatic ring), and Z ⁵¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-,- OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH2-COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (wherein, Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C - or a single bond, M ⁵¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any hydrogen atom of all 1,4-phenylene groups in the formula may also be fluorine Atomic substitution)

X ⁵¹ and X ⁵² each represent a diacrylate derivative of a hydrogen atom, and a dimethacrylate derivative each having a methyl group, and preferably one of which represents a hydrogen atom and the other represents a methyl group. . Regarding the polymerization rate of the compounds, the diacrylate derivative is the fastest, the dimethacrylate derivative is slow, and the asymmetric compound is used therebetween, and the preferred aspect can be used depending on the use thereof. Among the PSA display elements, a dimethacrylate derivative is particularly preferred.

Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -, and in the PSA display element, at least one of them is a single bond, and Preferably, all of the compounds represent a single bond or one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s . In this case, an alkyl group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

Z ^{51 is} preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or The key is more preferably -COO-, -OCO- or a single bond, and particularly preferably a single bond.

M ⁵¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom, and is preferably a 1,4-phenylene group or a single bond. In the case where C represents a ring structure other than a single bond, Z ^{51 is} also preferably a linking group other than a single bond. When M ⁵¹ is a single bond, Z ^{51 is} preferably a single bond.

In these terms, in the general formula (V), the ring structure between Sp ¹ and Sp ² is specifically preferably the structure described below.

In the general formula (V), when M ⁵¹ represents a single bond and the ring structure is formed of two rings, it preferably represents the following formula (Va-1) to formula (Va-5), more preferably The expression (Va-1) to the formula (Va-3) is particularly preferably expressed by the formula (Va-1).

(In the formula, it is assumed that both ends are bonded to Sp ¹ or Sp ² ).

The alignment control force after polymerization of the polymerizable compound containing these skeletons is most suitable for a PSA type liquid crystal display element, and a good alignment state can be obtained, so that display unevenness is suppressed or not at all produce.

In view of the above, as the polymerizable compound, the formula (V-1) to the formula (V-4) are particularly preferable, and among them, the formula (V-2) is most preferable.

(wherein, Sp ² represents an alkylene group having 2 to 5 carbon atoms).

When a polymerizable compound is added to the liquid crystal composition in the liquid crystal display device of the present invention, the polymerization is carried out even in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzil ketals, and fluorenylphosphine oxides.

In the liquid crystal display device of the present invention, the liquid crystal composition containing the polymerizable compound is polymerized by ultraviolet irradiation to impart a liquid crystal alignment ability, and can be used for controlling light by utilizing birefringence of the liquid crystal composition. A liquid crystal display element that transmits light. As a liquid crystal display element, it can be used for AM-LCD (Active Matrix Liquid Crystal Display Element), TN (Nematic Liquid Crystal Display Element), STN-LCD (Super Torsional Nematic Liquid Crystal Display Element), OCB-LCD, and IPS-LCD (Transverse electric field effect liquid crystal display element), especially for AM-LCD, can be used for a transmissive or reflective liquid crystal display element.

(curable resin composition)

The sealant in the liquid crystal display device of the present invention is composed of a cured product of a curable resin composition containing at least one compound of at least one (meth)acryl group and an epoxy group in one molecule.

The compound having at least one or more (meth)acrylic groups and epoxy groups in the above-mentioned one molecule is not particularly limited, and examples thereof include a (meth)acrylic modified epoxy resin and an urethane modified product. A (meth)acrylic epoxy resin or the like.

(1) (meth)acrylic modified epoxy resin

The (meth)acrylic acid-modified epoxy resin is not particularly limited, and can be obtained, for example, by reacting (meth)acrylic acid with an epoxy resin in the presence of a basic catalyst according to a usual method.

As the (meth)acrylic acid-modified epoxy resin, for example, a part (meth)acrylic acid such as a novolac type epoxy resin or a bisphenol type epoxy resin is used, and as the epoxy resin, it is preferred to be an epoxy resin. A benzene type epoxy resin, a naphthalene type epoxy resin, a tris(hydroxyphenyl)alkyl type epoxy resin, a tetrakis (hydroxyphenyl) alkyl type epoxy resin, or the like.

The epoxy compound to be used as a raw material for synthesizing the above (meth)acrylic acid-modified epoxy resin is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a bisphenol E type epoxy resin, and a bisphenol F type. Epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, polyoxypropylene bisphenol A type epoxy resin, epoxy Propane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy Resin, naphthalene epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenol novolak epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol aldehyde varnish Epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, epoxy propyl ester compound, bisphenol A type of episulfide resin, alicyclic epoxy resin, and the like. Among them, preferred are bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, phenol novolak epoxy resin, Phenylene ether type epoxy resin.

For example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation) and EPICLON 850-S (manufactured by DIC Corporation) are commercially available as an epoxy compound which is a raw material for the synthesis of the epoxy (meth) acrylate. Bisphenol A epoxy resin such as bisphenol A epoxy resin, jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation), bisphenol E epoxy resin such as R-710, EPICLON EXA1514 (made by DIC) Hydrogenated bisphenol epoxy resin such as 2,2'-diallyl bisphenol A epoxy resin such as phenol S-type epoxy resin or RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and EPICLON EXA7015 (manufactured by DIC Corporation) Propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (made by ADEKA), resorcinol type epoxy resin such as EX-201 (made by Nagasechemtex), jERYX-4000H (manufactured by Mitsubishi Chemical Corporation) Biphenyl type epoxy resin such as biphenyl type epoxy resin, YSLV-50TE (manufactured by Nippon Steel Chemical Co., Ltd.), phenyl ether type epoxy resin such as YSLV-80DE (manufactured by Nippon Steel Chemical Co., Ltd.), EP-4088S Dicyclopentadiene type epoxy resin such as (made by ADEKA), EPICLON HP4032, EPICLON EX A-4700 (all manufactured by DIC Corporation) Phenolic novolac type epoxy resin such as naphthalene type epoxy resin, EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), jER152, jER154 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-670-EXP -Sphenol (phenolic varnish type epoxy resin) such as -S (manufactured by DIC), Epiclon N660, EPICLON N665, EPICLON N670, EPICLON N673, EPICLON N680, EPICLON N695, EPICLON N665EXP, EPICLON N672EXP (manufactured by DIC), etc. a varnish-type epoxy resin, a dicyclopentadiene novolac type epoxy resin such as EPICLON HP7200 (manufactured by DIC Corporation), a biphenol novolak type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), and ESN-165S ( Naphthol phenol novolac type epoxy resin, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc. Epoxy resin, ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Epolight 80MFA (Kyoeisha Chemical Co., Ltd.) Alkyl polyol type epoxy resin such as DENACOL EX-611, manufactured by Nagasechemtex, YR-450, YR-207 (all manufactured by Nippon Steel Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Co., Ltd.), etc. Rubber modified epoxy resin, epoxy propyl ester compound such as DENACOL EX-147 (manufactured by Nagasechemtex), bisphenol A type episulfide resin such as jERYL-7000 (manufactured by Mitsubishi Chemical Corporation), and other YDC-1312, YSLV- 80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EX A-7120 (manufactured by DIC Corporation), TEPIC (Nissan Chemical Co., Ltd.) Manufacturing) and so on. In addition, the alicyclic epoxy resin is not particularly limited, and examples of the commercially available product include Celloxide 2021, Celloxide 2080, Celloxide 3000, Epolead GT300, and EHPE (all manufactured by Daicel Co., Ltd.).

Specific examples of the epoxy (meth) acrylate include resorcinol type epoxy acrylate by resorcinol type epoxy resin ("EX-201", manufactured by Nagasechemtex Co., Ltd.) 360 weight. 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid, while air was blown, and refluxed at 90 ° C for 5 hours. And get.

Further, examples of the commercially available epoxy (meth) acrylate include Ebecryl 860, Ebecryl 1561, Ebecryl 3700, Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl 3200, Ebecryl 3201, Ebecryl 3702, and Ebecryl 3412. , Ebecryl 860, Ebecryl RDX63182, Ebecryl 6040, Ebecryl 3800 (both manufactured by Daicel Cytec), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all Xinzhongcun Chemical Manufactured by Industrial Co., Ltd., EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA Manufacturing), DENACOL Acrylate DA -141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagasechemtex Co., Ltd.), and the like.

(2) Amine ester modified (meth)acrylic epoxy resin

The above amine ester-modified (meth)acrylic epoxy resin is obtained, for example, by the following method. That is, a method in which a polyol is reacted with a bifunctional or higher isocyanate to further react the obtained reaction with a (meth)acrylic monomer having a hydroxyl group and dehydrated glycerin; or a polyol is not used; A method of reacting a functional or higher isocyanate with a (meth)acrylic acid monomer having a hydroxyl group or dehydrated glycerin; or a method of reacting a (meth) acrylate having an isocyanate group with dehydrin or the like. Specifically, for example, by first reacting trimethylolpropane 1 mol with isophorone diisocyanate 3 mol under a tin-based catalyst, an isocyanate group remaining in the obtained compound can be used as a It is produced by reacting hydroxyethyl acrylate having a hydroxyl group-containing acrylic monomer and dehydrin which is an epoxide having a hydroxyl group.

The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, glycerin, sorbitol, trimethylolpropane, and (poly)propylene glycol.

The isocyanate is not particularly limited as long as it is a bifunctional or higher functional group, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and the like. Methylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Benzyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10 - undecane triisocyanate or the like.

The (meth)acrylic monomer having a hydroxyl group is not particularly limited, and examples of the monomer having one hydroxyl group in the molecule include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of the monomer having two or more hydroxyl groups in the molecule, such as an ester or a hydroxybutyl (meth)acrylate, may be an epoxy such as bisphenol A modified epoxy (meth) acrylate. Base) acrylate. These may be used alone or in combination of two or more.

The epoxy group of the curable resin composition and the (meth)acrylic group are preferably an acrylic group: the epoxy group is 40:60 to 95:5. When the equivalent ratio of the (meth)acrylic group is less than 40, the photoreactivity is lowered, and even if the sealant is irradiated with light after adjusting the gap, there is no initial temporary hardening, and not only the liquid crystal The elution is also large, and if it exceeds 95, it may be insufficient in terms of adhesion or moisture permeability. The blend ratio of the epoxy group to the (meth)acrylic group is more preferably from 50:50 to 80:20.

In order to reduce the compatibility with the liquid crystal, the contamination is eliminated, and the problem of poor display such as whitening, uneven alignment, and image sticking is suppressed, and at least one or more (meth)acrylic groups and epoxy groups are contained in the above-mentioned one molecule. The compound preferably has a hydrogen bond group, and for example, preferably has a hydroxyl group and/or an amine ester bond.

The compound having at least one or more (meth)acrylic group and epoxy group in the above-mentioned one molecule preferably has a moiety selected from a biphenyl skeleton, a naphthalene skeleton, a bisphenol skeleton, and a novolak-type epoxy resin (methyl group). At least one molecular skeleton of the acrylate. Thereby, the heat resistance of the curable resin composition of the present invention is improved.

The number average molecular weight of the compound having at least one (meth)acrylic group and the epoxy group in each of the above molecules is preferably 300 or more. If it is less than 300, it will elute into a liquid crystal, and it will become easy to disorder. Further, the number average molecular weight is preferably 3,000 or less. If it exceeds 3,000, the adjustment of the viscosity becomes difficult.

When a compound having at least one (meth)acrylic group and an epoxy group in each of the above-mentioned molecules is used as the curable resin, the infrared absorbing property is measured after the curable resin composition of the first invention is cured. The spectrum was found to be the absorption peak derived from the carbonyl group of the (meth)acryl group. Further, when an epoxy group and a hydroxyl group derived from an epoxy group are present, the absorption peak can also be observed.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules preferably has a hydrogen bond functional group value of from 3 × 10 ^-3 to 5 × 10 ^{-3 .} Mol/g. Since the curable resin composition forms a hydrogen bond in the molecule, when it is used as a sealant, it becomes difficult to elute into the liquid crystal before and after hardening, and it is difficult to cause liquid crystal contamination, and suppression of whitening and alignment can be suppressed. It is preferable that unevenness, residual image, and the like are poorly displayed.

The above hydrogen bond is obtained by containing a functional group or a residue having a hydrogen bond, for example, having an -OH group, an -NH 2 group, or a -NHR group (R represents an aromatic, an aliphatic hydrocarbon or a derivative thereof) a functional group such as a -COOH group, a -CONH2 group or a -NHOH group, or a compound having a residue such as a -NHCO- bond, a -NH- bond, a -CONHCO- bond, or a -NH-NH- bond in the molecule. . In addition, when the hydrogen bond functional group value is one type of the compound having a hydrogen bond functional group, the value calculated by the following (Formula 1) is used.

Hydrogen bond functional group value (HX) (mol/g) = (number of hydrogen bond functional groups in one molecule of compound X) / (molecular weight of compound X) (formula 1)

Further, in the case where the above-mentioned hydrogen bond functional group value is composed of a mixture of a plurality of resins having a hydrogen bond functional group, the content per unit weight of each compound having a hydrogen bond functional group (weight basis) Rate) is assigned and calculated. For example, the hydrogen bond functional group value in the case where the compound having a hydrogen bond functional group is composed of the compound A, the compound B, and the compound C is represented by the following (formula 2).

Hydrogen bond functional group value (H _ABC )=H _A P _A +H _B P _B +H _C P _C (Formula 2)

(Further, P α represents the weight fraction of the compound α).

When the hydrogen bond functional group value is less than 3 × 10 ^-3 mol/g, the curable resin composition component is eluted into the liquid crystal, and the alignment of the liquid crystal is easily disturbed, and if it exceeds 5 × 10 ^-3 mol/g, Then, the moisture permeability of the cured product becomes large, and the moisture easily enters the inside of the liquid crystal display element.

The compound having a hydrogen bond functional group may have a hydrogen bond functional group value in the above range, or may be adjusted to the above range by mixing two or more types. Surrounding. That is, the average value of the hydrogen bond functional group values of the compound having a hydrogen bond functional group used may be in the above range.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules preferably has a volume resistivity after curing of 1 × 10 ¹³ Ω ‧ cm or more. If it is less than 1 × 10 ¹³ Ω ‧ cm, it means that the sealant contains ionic impurities, and when used as a sealant, ionic impurities are eluted into the liquid crystal during energization, and the voltage retention ratio of the liquid crystal layer (VHR) The decrease, the increase in ion density, and the reasons for poor display, such as anti-white, misalignment, and residual image.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules preferably has a specific resistance of 1.0 × 10 ⁶ to 1.0 × 10 ¹⁰ Ω · cm before curing. . When it is less than 1.0 × 10 ⁶ Ω ‧ cm, when the liquid crystal is eluted when used as a sealant, the voltage holding ratio (VHR) of the liquid crystal layer is lowered, the ion density is increased, and Reasons such as uneven alignment, residual image, etc. When it exceeds 1.0 × 10 ¹⁰ Ω ‧ cm, the adhesion to the substrate may be inferior.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above-mentioned molecules may further contain a resin having a (meth)acryloxy group and/or having an epoxy group. As the resin, the resin described in the "resin having a (meth)acryloxy group) and the "resin having an epoxy group" described below can be used. In either case, the preferred upper limit of the ratio of the epoxy group to the total amount of the (meth)acrylic group and the epoxy group is 40 mol%. When it exceeds 40 mol%, the solubility in a liquid crystal becomes high, and display characteristics fall.

(resin having (meth)acryloxy group)

The resin having a (meth) acryloxy group is a resin described below. For example, an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, (meth)propyl group obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group can be mentioned. Ethyl amide and the like.

(1) an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group

The ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group is not particularly limited, and examples of the monofunctional one include 2-hydroxyethyl (meth)acrylate and (methyl). ) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( Isooctyl methacrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate 2 - methoxyethyl ester, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, benzyl (meth) acrylate, Ethyl diglycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate , methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ( Methyl)acrylic acid 1H, 1H, 5H-octafluoropentane , (meth)acrylic acid ylide, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate Butyl ester, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate, isomyristate (meth)acrylate Ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, ( Diethylaminoethyl methacrylate, dimethylaminoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene decyloxy Ethyl hexahydrophthalic acid, 2-(methyl) propylene oxiranyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2-(methyl) propylene oxide Ethyl ethyl ester and the like.

Further, as described above, by (meth)acrylic acid and a compound having a hydroxyl group The bifunctional group of the ester compound to be obtained is not particularly limited, and examples thereof include 1,4-butanediol di(meth)acrylate and 1,3-butanediol di(meth)acrylate. 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 2-N-butyl Benzyl-2-methyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide Addition of bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dihydroxyl Dicyclopentadiene di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified heterotrimerization Di(meth) acrylate cyanate, 2-hydroxy-3-propenyl methoxy propyl di(meth) acrylate, Carbonate diol di(meth) acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, Polybutadienediol di(meth)acrylate or the like.

In addition, the above-mentioned ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group is not particularly limited, and examples thereof include pentaerythritol tri(meth)acrylate. Trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, Caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition tris (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, neopentyl alcohol tetra(meth) acrylate, glycerol tri(meth) acrylate, ring Oxypropane is added to tris(meth)acrylate, tris(methyl)propenyloxyethyl phosphate, and the like.

(2) an amine (meth)acrylate obtained by reacting an isocyanate with an acrylic acid derivative having a hydroxyl group

The (meth)acrylic acid amine ester obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and for example, one equivalent of the compound having two isocyanate groups can be obtained. Two equivalents of a hydroxyl group (meth)acrylic acid derivative are obtained by reacting in the presence of a tin-based compound as a catalyst.

The isocyanate which is a raw material of the (meth)acrylic acid amine ester obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include isophorone diisocyanate. 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI , polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, three (Isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,10-undecane triisocyanate, and the like.

In addition, as the isocyanate which is a raw material of the (meth)acrylic acid amine ester obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group, for example, ethylene glycol, glycerin or sorbose can also be used. Chain extended by reaction of a polyol such as an alcohol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and an excess of isocyanate Isocyanate compound.

The (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4. - Commercial products such as hydroxybutyl ester and 2-hydroxybutyl (meth)acrylate or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, polyethylene a mono (meth) acrylate or a di(meth) acrylate of a trihydric alcohol such as a monohydric alcohol such as a diol, a trimethylolethane, a trimethylolpropane or a glycerin, Bisphenol A is modified with an epoxy (meth) acrylate such as epoxy (meth) acrylate.

The above-mentioned (meth) acrylate can be, for example, due to trimethylol To 134 parts by weight of propane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate were added, and the mixture was refluxed at 60 ° C while stirring. The reaction was carried out for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate was added, and the mixture was stirred under reflux at 90 ° C while being blown with air for 2 hours.

Moreover, as a commercial item of the above-mentioned (meth)acrylic acid amide, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Ebecryl 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402, Ebecryl 8804, Ebecryl 8803, Ebecryl 8807, Ebecryl 9260, Ebecryl 1290, Ebecryl 5129, Ebecryl 4842, Ebecryl 210, Ebecryl 4827, Ebecryl 6700, Ebecryl 220, Ebecryl 2220 (all manufactured by Daicel Cytec) , Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensei Industrial Co., Ltd.), U -122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA , UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U -6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-1011, UA-306T, UA-3061, etc.

In addition, in order to further suppress elution of the component for liquid crystal dropping method of the present invention to the liquid crystal before curing, the curable resin preferably has at least one hydrogen bond functional group in one molecule.

The hydrogen bond functional group is not particularly limited, and examples thereof include an -OH group, a -SH group, and a -NHR group (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof), a -COOH group, a functional group such as -NHOH group, and a residue such as -NHCO-, -NH-, -CONHCO-, -NH-NH- present in the molecule, wherein -OH is preferred in terms of ease of introduction. base.

Further, the sealant of the present invention may contain a resin having an epoxy group.

The epoxy group-containing resin is not particularly limited, and examples thereof include an epichlorohydrin derivative, a cyclic aliphatic epoxy resin, and a compound obtained by a reaction of an isocyanate with dehydrin.

The epoxy group-containing resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diallyl double. Phenolic A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin , diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac varnish Type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy propyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, A glycidyl ester compound, a bisphenol A type episulfide resin, or the like.

Examples of the epichlorohydrin derivative include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850-S (manufactured by DIC Corporation), bisphenol A type epoxy resin, jER806, and jER4004 (all are Mitsubishi Chemical Corporation). 2,2'-diallyl bisphenol such as bisphenol S type epoxy resin such as bisphenol F type epoxy resin, EPICLON EXA1514 (manufactured by DIC Corporation), and RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) A type epoxy resin, hydrogenated bisphenol type epoxy resin such as EPICLON EXA7015 (manufactured by DIC Corporation), propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (made by ADEKA), and EX-201 (Nagasechemtex Manufactured) Resorcinol type epoxy resin, biphenyl type epoxy resin such as jERYX-4000H (manufactured by Mitsubishi Chemical Corporation), sulfide type epoxy resin such as YSLV-50TE (manufactured by Nippon Steel Chemical Co., Ltd.), YSLV- Dicyclopentadiene type epoxy resin such as BDE (manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin such as EP-4088S (made by ADEKA), EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation) ) naphthalene type epoxy resin, EPICLON N-770 (DIC Manufactured by a phenol novolac type epoxy resin, an o-cresol novolak type epoxy resin such as EPICLON N-670-EXP-S (manufactured by DIC Corporation), or a dicyclopentadiene phenol aldehyde such as EPICLON HP7200 (manufactured by DIC Corporation) Lacquer-type epoxy resin, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), etc., such as a non-phenol novolak type epoxy resin, ESN-165S (manufactured by Nippon Steel Chemical Co., Ltd.), naphthol novolak type epoxy resin, jER630 (Mitsubishi Epoxypropylamine type epoxy resin such as EPICLON 430 (manufactured by DIC), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), EPICLON 726 (DIC) Alkyd type epoxy resin, YR-450, YR-207, etc., manufactured by Nippon Steel Chemical Co., Ltd., Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Nagasechemtex Co., Ltd.) ), a rubber-modified epoxy resin such as Epolead PB (manufactured by Daicel), a epoxidized propyl ester compound such as DENACOL EX-147 (manufactured by Nagasechemtex), and a bisphenol A ring such as jERYL-7000 (manufactured by Mitsubishi Chemical Corporation) Sulfur resin, other YDC-1312, YSLV-80XY, YSLV-90CR (all new days) Chemical Corporation), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (both manufactured by Mitsubishi Chemical Corporation), EX A-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co.) and the like.

In addition, the cyclic aliphatic epoxy resin is not particularly limited, and examples of the commercially available product include Celloxide 2021, Celloxide 2080, Celloxide 3000, Epolead GT300, and EHPE (all manufactured by Daicel Co., Ltd.).

The compound obtained by the reaction of the above isocyanate with dehydrin is not particularly limited, and for example, one equivalent of the compound having two isocyanate groups and two equivalents of deglycerin can be used in the presence of a tin-based compound as a catalyst. Obtained by carrying out the reaction.

The isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene group. Diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diiso Cyanate ester, benzodimethyl diisocyanate (XDI), hydrogenated XDI, quaternary acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, tetramethyl xylene diisocyanate, 1 6,10-undecane triisocyanate, and the like.

Further, as the above isocyanate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, poly propylene can also be used. A chain extended isocyanate compound obtained by the reaction of a polyol such as a lactone diol with an excess of isocyanate.

Further, the epoxy group-containing resin may be, for example, a resin having a (meth)acryloxy group and an epoxy group in one molecule. As such a compound, for example, a partially modified (meth)acrylic acid epoxy resin obtained by reacting a partial epoxy group of a compound having two or more epoxy groups with (meth)acrylic acid may be mentioned.

In addition, the curable resin may be one containing only the above-mentioned resin having a (meth)acryloxy group and an epoxy group in one molecule.

The above-mentioned partial (meth)acrylic acid-modified epoxy resin can be obtained, for example, by reacting an epoxy resin with (meth)acrylic acid in the presence of a basic catalyst according to a usual method. Specifically, for example, 190 g of a phenol novolac type epoxy resin ("N-770" manufactured by DIC Corporation) can be dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine is added to the solution to prepare a homogeneous solution. 35 g of acrylic acid was added dropwise to the solution under reflux for 2 hours, and further reflux stirring was carried out for 6 hours, followed by removal of toluene, whereby a phenol novolak type portion obtained by reacting 50 mol% of an epoxy group with acrylic acid was obtained. Acrylic modified epoxy resin (in this case, 50% is partially acrylated).

As a part of the above-mentioned partial (meth)acrylic acid-modified epoxy resin, UVACURE 1561 (manufactured by Daicel Cytec Co., Ltd.) is mentioned.

The curable resin composition containing a compound having at least one or more (meth)acrylic groups and an epoxy group in each of the above molecules preferably contains a curing agent. Among them, preferably Contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and is preferably a radical photopolymerization initiator, particularly a phenylalkylketone photopolymerization initiator, an oxime ester photopolymerization initiator, and a fluorenylphosphine oxide. A polymerization initiator is preferred.

Examples of the photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-1,2-diphenylethan-1-one. 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, benzhydryl isopropyl ether, benzoin dimethyl condensate Ketone, 1-hydroxycyclohexyl phenyl ketone, 9-oxo sulphur 1,2-octanedione 1-[4-(phenylthio)-2-(o-phenylmercaptopurine)]. These photopolymerization initiators may be used alone or in combination of two or more.

Further, a photopolymerization initiator having a reactive double bond and a photoreaction starting portion can also be used. Among them, a benzoin (ether) compound having a reactive double bond and a hydroxyl group and/or an amine ester bond is preferred. Further, the benzoin (ether) compound means benzoin and benzoin ether.

Examples of the reactive double bond include a residue such as an allyl group, a vinyl ether group, or a (meth)acrylic group. When used as a photopolymerization initiator for a sealant, the reactivity is high. The (meth)acrylic acid residue is preferred. By having this reactive double bond, weather resistance is improved.

The benzoin (ether)-based compound may have either a hydroxyl group or an amine ester bond, or both. When the benzoin (ether)-based compound does not have both a hydroxyl group and an amine ester bond, it may be dissolved in the liquid crystal before being hardened when it is blended in the sealant.

In the above benzoin (ether)-based compound, the reactive double bond and the hydroxyl group and/or the amine ester bond may be located in any part of the benzoin (ether) skeleton, but have the following formula (1-A). The molecular skeleton is preferred. When a compound having the molecular skeleton is used as a photopolymerization initiator, the amount of the residue is reduced, and the amount of external air can be reduced.

In the formula, R represents hydrogen and an aliphatic hydrocarbon residue having 4 or less carbon atoms. When R is an aliphatic hydrocarbon residue having a carbon number of 4, the storage stability when the photopolymerization initiator is blended is increased, but the reactivity is lowered due to the steric hindrance of the substituent.

The amount of the photopolymerization initiator to be added is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the curable resin. When the amount is less than 0.1 part by weight, the photopolymerization ability is insufficient, and the effect is not obtained. When the amount is more than 10 parts by weight, the unreacted photopolymerization initiator remains in a large amount, and the weather resistance is deteriorated. The amount of the photopolymerization initiator to be added is more preferably from 1 to 5% by weight.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules preferably further contains a thermosetting agent. The thermosetting agent is used to react and bond the epoxy group and/or the acryl group in the curable resin composition by heating, and to improve the adhesion and moisture resistance of the curable resin composition after curing. The role. The thermal curing agent is not particularly limited, and a latent thermal curing agent having a melting point of 100 ° C or higher can be preferably used. When a thermal curing agent having a melting point of 100 ° C or less is used, the storage stability is remarkably deteriorated.

Examples of such a thermosetting agent include an anthracene compound such as 1,3-bis[mercaptocarbonylethyl-5-isopropylhydantoin], dicyandiamide, an anthracene derivative, and 1-cyanoethyl b. 2-phenylimidazole, N-[2-(2-methyl-1-imidazolyl)ethyl]urea, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')]-Ethyl-symmetric three , N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'-(2-methyl-1-imidazolylethyl)-hexanediamine, 2-phenyl Imidazole derivatives such as 4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, modified aliphatic polyamine, tetrahydrophthalic anhydride, ethylene glycol - An acid anhydride such as ethylene glycol-bis (anhydrotrimellitate), an addition product of various amines and an epoxy resin, and the like. These may be used alone or in combination of two or more.

When an acrylic modified epoxy resin is used as the compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules, the reactivity of the acrylic epoxy resin changes greatly compared to its structure. In the case of an amine ester modified epoxy resin, due to its stability, even if a highly reactive thermosetting agent is used, storage stability is excellent, but in the case of (meth)acrylic acid modified epoxy resin The reactivity is high, and in terms of storage stability, a thermal hardener having a lower melting point of 100 ° C or higher is more preferable.

The blending ratio of the above-mentioned thermosetting agent is preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the curable compound. When it is outside the above range, the adhesion of the cured product and the chemical resistance are lowered, and the deterioration of the characteristics of the liquid crystal in the high-temperature and high-humidity operation test is advanced.

Further, as the above-mentioned thermosetting agent, the following coating thermosetting agent is preferable. When the coated heat-curing agent of the present invention is used, very high storage stability can be obtained even as a one-liquid type.

In other words, by using a coated heat-curing agent which is coated with a surface of a solid heat-hardening agent by a particle which lacks volatility and lacks solubility to an organic substance, it is possible to obtain a seal having extremely high storage stability even if a curing agent is previously blended. Agent.

In the present specification, the solid heat hardener refers to a hardener which is solid at room temperature, melts or softens by heating, and starts to react with the curable resin. The solid heat curing agent is not particularly limited as long as it has a melting point or a softening point of room temperature or higher, and examples thereof include a solid amine compound, a phenol compound, and an acid anhydride. Among them, a solid amine compound is preferred in terms of excellent reactivity at a low temperature.

The above solid amine compound means a solid having one or more amine groups of 1 to 3 in the molecule. Examples of the compound compound include aromatic amines such as m-phenylenediamine and diaminodiphenylmethane, 2-methylimidazole, 1,2-dimethylimidazole, and 1-cyanoethyl-2-methylimidazole. An imidazole compound, an imidazoline compound such as 2-methylimidazoline, a diterpene azelaic acid or a diterpene isophthalate compound. As an example of such a solid amine compound, an amine addition product such as Amicure PN-23, Amicure MY-24, (above, Ajinomoto Fine-Techno Co., Ltd.), dicyandiamide, etc. are mentioned.

Examples of the polyphenol-based compound include a polyphenol compound and a novolac type phenol resin. For example, jER CURE 170, jER CURE YL6065, jER CURE MP402FPI (above, manufactured by Mitsubishi Chemical Corporation), and the like are mentioned as a commercially available one.

Examples of the acid anhydride include glycerin bis(hydrogen trimellitate), ethylene glycol-bis (hydrogen trimellitate), tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. -methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, and the like. For example, jER CURE YH-306, YH-307 (above, manufactured by Mitsubishi Chemical Corporation), and the like are mentioned as a commercially available one.

The average particle diameter of the solid thermosetting agent particles is not particularly limited, but is preferably 0.1 to 50 μm. When the thickness is less than 0.1 μm, the surface may not be efficiently coated by the fine particles. When the thickness exceeds 50 μm, precipitation of the curing agent may occur during storage, or hardening unevenness may occur. The average particle diameter of the above solid heat hardener particles is more preferably 0.5 to 10 μm.

Examples of the fine particles on the surface of the coated solid thermosetting agent particles include oxides such as Si, Al, Ti, Fe, Mn, and Mg, hydroxides, halides, styrene beads, and particulate rubber. These fine particles may be used singly or in combination of two or more.

The average particle diameter of the fine particles is preferably 0.05 μm or less. When it exceeds 0.05 μm, the surface of the solid heat hardener particles may not be efficiently coated. The average particle diameter of the above fine particles is more preferably 0.03 μm or less. Further, the particle diameter of the fine particles is preferably 10% or less of the particle diameter of the solid thermosetting agent particles. If it is 10% or more, there is a case where the control ability of the reactivity is not sufficiently exhibited.

The weight ratio of the solid thermosetting agent particles to the fine particles in the coating thermosetting agent is preferably from 50:1 to 3:1. When the weight ratio of the solid thermosetting agent particles exceeds 50, the control ability of the reactivity may not be sufficiently exhibited. If it is less than 3, the fine particles may be excessively present and the hardening function may be lowered. The weight ratio of the solid thermosetting agent particles to the fine particles in the coated thermosetting agent is preferably from 20:1 to 5:1.

The method of coating the surface of the solid heat hardener particles by the fine particles is not particularly limited, and for example, a solid heat hardener particle and fine particles are mixed in a container and uniformized by using a commercially available blender or the like. Method, etc.

The blending ratio of the curable resin composition to the coating thermosetting agent is preferably from 1 to 100 parts by weight based on 100 parts by weight of the curable resin composition. When it is less than 1 part by weight, it may not be sufficiently cured. If it exceeds 100 parts by weight, an excessive amount of the thermal curing agent remains, and various physical properties such as toughness of the obtained cured product may be lowered.

When the coated thermosetting agent is blended in the curable resin composition, the contact between the solid thermosetting agent and the polymerizable resin is suppressed by the fine particles on the surface during storage at room temperature, thereby exhibiting high storage stability and application at the time of curing. The temperature is such that the solid thermosetting agent becomes liquid without being inhibited by the fine particles, thereby coming into contact with the curable resin, and the hardening reaction is quickly started. Therefore, the storage stability of the curable resin composition is improved. The above-mentioned coated thermal curing agent can be produced extremely simply at a normal temperature and for a short period of time without using a special reaction.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules may further contain a radical polymerization inhibitor.

Examples of the above radical polymerization inhibitor include 2,6-di-tertiary butyl cresol, butylated hydroxyanisole, 2,6-di-tertiary butyl-4-ethylphenol, and stearyl β. -(3,5-di-tributyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2 '-Methylene bis(4-ethyl-6-tributyl phenol), 4,4'-thiobis-3-methyl-6-tertiary butyl phenol, 4,4-butylene double (3-methyl-6-tertiary butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methyl) Phenyl)propenyloxy]ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane, tetra-[methylene-3-(3',5'-di -Tris-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-symmetric three -2,4,6-(1H,3H,5H)trione, hydroquinone, p-methoxyphenol, and the like. These radical polymerization inhibitors may be used alone or in combination of two or more.

The blending amount of the radical polymerization inhibitor is 0.1 part by weight and the upper limit is 0.4 part by weight based on 100 parts by weight of the curable resin composition. When the amount of the above-mentioned radical polymerization inhibitor is less than 0.1 part by weight, the radical polymerization inhibitor is rapidly consumed by the radical which is rarely generated when the weak light is generated in the production of the liquid crystal display element, and is erroneously The hardening of the sealant is hardened when exposed to weak light. When the blending amount of the radical polymerization inhibitor exceeds 0.4 parts by weight, the ultraviolet curability of the obtained sealant is remarkably low, and it is not cured even when the ultraviolet ray is irradiated to cure the sealant.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules preferably further contains a decane coupling agent. The decane coupling agent mainly functions as a bonding aid for adhering the sealing agent to the liquid crystal display element substrate well. Further, there is a case in which an inorganic or organic filler blended with a resin constituting the sealant is blended in order to improve the adhesion to the stress dispersion effect, the improvement in the coefficient of linear expansion, and the like. The surface of the filler is treated with a decane coupling agent.

The decane coupling agent is preferably a decane compound having at least one functional group represented by the following group (2-A) and at least one functional group represented by the following group (2-B).

(2-A)-OCH ₃ -OC ₂ H ₅

Specific examples of the decane compound include γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-. Isocyanatopropyltrimethoxydecane, and the like. These decane compounds may be used singly or in combination of two or more.

By using a decane compound having such a structure as a decane coupling agent, adhesion to a substrate can be improved, and a decane compound is chemically bonded to a curable resin via a functional group represented by a group 1-B, thereby preventing migration into a liquid crystal. Flow out.

The decane compound and the curable resin component are blended and then subjected to heat treatment. The decane compound is chemically bonded to the curable resin component via a functional group represented by a group 1-B by heat treatment. In the above heat treatment, it is preferred to carry out the above heat treatment by stirring the resin mixture in order to increase the efficiency of the reaction. The method of stirring is not particularly limited, and examples thereof include a stirrer or a usual method of rotating a blade for stirring by a motor or the like. The temperature of the heat treatment is preferably from 30 to 70 °C. If the temperature is less than 30 ° C, the reaction between the decane compound and the curable resin may not proceed sufficiently. If it exceeds 70 ° C, the curing by heat may be started. The temperature of the heat treatment is more preferably 40 to 60 °C. The heat treatment time is preferably from 1 to 2 hours. If it is less than 1 hour, all of the functional groups in the decane compound are unreacted and the unreacted material remains.

The residual ratio of at least one functional group represented by the above 1-B group after the heat treatment is 10% or less. When it exceeds 10%, it will react with a resin component during storage, and it will become thick, or it will flow out in a liquid-crystal, and it is a contamination. Further, the residual ratio of at least one functional group represented by the 1-B group can be determined by 1H-NMR, and the relative ratio of the peak intensity of each functional group in the decane compound to the peak intensity after heat treatment is determined. .

In order to adjust the viscosity and improve the adhesion using the stress dispersion effect, the above A filler may be added to the curable resin composition of a compound having at least one (meth)acrylic group and an epoxy group in one molecule.

The filler is not particularly limited, and for example, talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, zinc oxide, iron oxide, or the like may be used. Magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, inorganic fillers such as aluminum nitride, or polyester microparticles, Organic fillers such as polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, and rubber microparticles.

The shape of the filler is not particularly limited, and examples thereof include a shaped object such as a spherical shape, a needle shape, and a plate shape, or an amorphous material.

The curable resin composition containing a compound having at least one (meth)acrylic group and an epoxy group in each of the above molecules may further contain resin fine particles.

The resin fine particles have a core layer composed of a resin having rubber elasticity and a glass transition temperature of -10 ° C or lower, and a shell layer composed of a resin having a glass transition temperature of 50 to 150 ° C formed on the surface of the core particle. .

In the present specification, the glass transition temperature is not particularly limited, and means that it is measured by a normal DSC method at a temperature increase rate of 10 ° C/min.

The resin having rubber elasticity and having a glass transition temperature of -10 ° C or lower is not particularly limited, and a polymer of a (meth)acrylic monomer is preferred.

Examples of the (meth)acrylic monomer include ethyl acrylate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, and methacrylic acid. Ester and the like. These (meth)acrylic monomers may be polymerized alone or in combination of two or more.

The resin having a glass transition temperature of 50 to 150 ° C is not particularly limited, and examples thereof include isopropyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and A. A polymer obtained by polymerizing phenyl acrylate, methyl methacrylate, styrene, 4-chlorostyrene, 2-ethylstyrene, acrylonitrile, vinyl chloride or the like. These monomers may be used singly or in combination of two or more.

The particle diameter of the resin fine particles is appropriately selected depending on the purpose of use, and a preferred lower limit is 0.01 μm, and a preferred upper limit is 5 μm. Within this range, the surface area of the resin fine particles with respect to the photocurable resin is sufficiently large, and the swelling effect of the effective core layer is exhibited. Further, it is formed as a gap between the substrates when used as a sealing agent for a liquid crystal display element, and workability can be ensured.

The method for producing the resin fine particles is not particularly limited. For example, a core particle is formed by an emulsion polymerization method using only a monomer constituting a core, and then a monomer constituting the outer shell is further added to be polymerized, and the core particle is used. A method of forming a shell layer on a surface, and the like.

A preferred lower limit of the amount of the resin fine particles to be blended in the curable resin composition is 15 parts by weight based on 100 parts by weight of the photocurable resin, and a preferred upper limit is 50 parts by weight. If it is less than 15 parts by weight, a sufficient effect of improving the adhesion may not be obtained, and if it exceeds 50 parts by weight, the adhesion may be increased to more than necessary. A more preferable upper limit is 20 parts by weight.

(alignment film)

In the liquid crystal display device of the present invention, since the liquid crystal composition is aligned on the surface of the first substrate and the second substrate that is in contact with the liquid crystal composition, it is disposed in the color filter in the liquid crystal display device requiring the alignment film. Even if the thickness of the alignment film is as thin as 100 nm or less between the sheet and the liquid crystal layer, the interaction between the dye such as the pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer cannot be completely blocked.

Further, in the liquid crystal display device in which the alignment film is not used, the interaction between the dye such as the pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer becomes larger.

As the alignment film material, transparent organic materials such as polyimine, polyamine, BCB (benzocyclobutene polymer), polyvinyl alcohol or the like can be used. It is preferred to use a diamine such as an aliphatic or alicyclic diamine such as p-phenylenediamine or 4,4'-diaminodiphenylmethane, and butane tetracarboxylic anhydride or 2,3,5-three. A polyamidimide alignment film obtained by ruthenium imidization of a polyamic acid synthesized from an aromatic tetracarboxylic anhydride such as an aliphatic or alicyclic tetracarboxylic anhydride or a pyrogallic dianhydride such as carboxycyclopentyl acetic anhydride. In this case, the alignment imparting method generally uses friction, but when it is used for a vertical alignment film or the like, it may be used without imparting alignment.

As the alignment film material, a material containing chalcone, cinnamate, cinnamon or azo in the compound may be used, or may be used in combination with a material such as polyimine or polyamine. In this case, alignment The film can be rubbed or optically aligned.

In the alignment film system, the alignment film material is usually applied onto a substrate by a spin coating method or the like to form a resin film. However, a uniaxial stretching method, a Langmuir-Blodgett method, or the like may be used. .

(transparent electrode)

In the liquid crystal display device of the present invention, as the material of the transparent electrode, a conductive metal oxide can be used, and as the metal oxide, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), or zinc oxide can be used. ZnO), indium oxide (In ₂ O ₃ -SnO ₂ ), indium zinc oxide (In ₂ O ₃ -ZnO), cerium-added titanium dioxide (Ti _1-x Nb _x O ₂ ), fluorine-doped tin oxide, graphene A nanobelt or a metal nanowire or the like is preferably zinc oxide (ZnO), indium tin oxide (In ₂ O ₃ -SnO ₂ ) or indium zinc oxide (In ₂ O ₃ -ZnO). The patterning of the transparent conductive films may be performed by photolithography or a method using a mask.

The liquid crystal display device of the present invention is particularly useful for a liquid crystal display device for active matrix driving, and can be applied to a liquid crystal display device for a TN mode, an IPS mode, a polymer stabilized IPS mode, an FFS mode, an OCB mode, a VA mode, or an ECB mode.

The liquid crystal display device and the backlight device are combined and used for various purposes such as a liquid crystal television, a computer monitor, a mobile phone, a smart phone display, a notebook personal computer, a mobile information terminal, and a digital signage. As a backlight device, there is a cold cathode tube type backlight device, an analog white backlight device using a two-wavelength peak using an inorganic material-emitting light-emitting diode or an organic EL element. Backlight device with three-wavelength peaks, etc.

[Examples]

The invention is further described in detail below with reference to the examples, but the invention is not limited to the examples. Further, "%" in the compositions of the following examples and comparative examples means "% by mass".

In the examples, the measured characteristics are as follows.

T _ni : nematic phase-isotropic liquid phase transfer temperature (°C)

△n: refractive index anisotropy at 25 ° C

△ ε: dielectric anisotropy at 25 ° C

η: viscosity at 20 ° C (mPa.s)

γ 1: rotational viscosity at 25 ° C (mPa.s)

VHR: Voltage holding ratio at 70 ° C (%)

(The value of the ratio of the measured voltage to the initial applied voltage in the case where the liquid crystal composition is injected into a cell having a cell thickness of 3.5 μm and the measurement is performed under conditions of 5 V, a frame time of 200 ms, and a pulse width of 64 μs)

ID: ion density at 70 ° C (pC/cm ² )

(Injection of a liquid crystal composition in a cell having a cell thickness of 3.5 μm, and ion density value when measured by applying MTR-1 (manufactured by Toyo Co., Ltd.) under the conditions of application of 20 V and a frequency of 0.05 Hz)

Uneven alignment: In the energized state and the non-energized state, the grade of the unevenness of the alignment between the sealant and the liquid crystal was evaluated by visual inspection in four levels.

◎ unaligned uneven

○ There is very little uneven distribution, but it is a tolerable level

△ There is uneven alignment and it is unacceptable

×There is uneven alignment and is quite bad

Afterimage: The residual image evaluation of the liquid crystal display element was evaluated by displaying the specific fixed pattern for 1000 hours in the display area, and the level of the residual image of the fixed pattern when the entire screen was uniformly displayed was visually observed by the following four levels.

◎ no residual image

○ There are very few afterimages, but they are tolerable

△ There is residual image and it is an unacceptable level

× has residual image and is quite bad

Volume resistivity of the sealant after hardening: After the sealant is applied thinly and uniformly on the chromium vapor deposition surface of the chromium vapor-deposited glass substrate, ultraviolet curing is performed to form an ultraviolet cured product having a size of 85 mm × 85 mm and a thickness of 3 m. The chromium vapor-deposited surface was placed on the ultraviolet-cured side, and a chromium vapor-deposited glass substrate was placed thereon, and a load was applied thereto, and the mixture was heated and pressure-bonded on a hot plate at 120 ° C for 1 hour to prepare a test sample. The area of the sealant in the test sample was set to (S (cm ² )), and the chrome steamed on the chrome-deposited glass substrate was pressed using a constant pressure generating device (manufactured by Kenwood Co., Ltd., PA36-2A controlled DC power source). A certain voltage (V (V)) was applied between the plating surfaces, and the current flowing through the film (A (A)) was measured by an ammeter (Advantest, R644C digital multimeter). When the film thickness of the sealant was (T (cm)), the volume resistivity (?‧ cm) was determined by the following formula. Volume resistivity (Ω‧cm) = (V‧S) / (A‧T), wherein the applied voltage was set to DC 500V, and the conduction time was set to 1 minute.

Specific resistance of the sealant before hardening: For the sealant before hardening, in the standard temperature and humidity state (20 ° C, 65% RH), a specific resistance measuring device (manufactured by Toyo Corporation, model SR-6517) and a liquid electrode are used. (Manufactured by Ando Electric Co., Ltd., type LE-21) The specific resistance was measured.

Further, in the examples, regarding the description of the compounds, the following abbreviations are used.

(ring structure)

(side chain structure and joint structure)

[Production of Curable Resin Composition]

(Synthesis Example A) Synthesis of acrylic acid modified resorcinol type epoxy resin (A)

106 parts by weight of a resorcinol type epoxy resin (EX-201 manufactured by Nagasechemtex Co., Ltd.) and 0.1 part by weight of triphenylphosphine were uniformly dissolved in a solvent, and 32 parts by weight of acrylic acid was added dropwise under reflux for 2 hours. Further, reflux stirring was carried out for 8 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (Sillitin V85, manufactured by Hoffmann Mineral Co., Ltd.) to remove toluene. This gave 50% of a partially modified acrylic resorcinol type epoxy resin (A).

(Synthesis Example B) Synthesis of acrylic modified bisphenol A type epoxy resin (B)

1280 parts by weight of solid bisphenol A diglycidyl ether (EXA850CRP manufactured by DIC Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and 2 parts by weight of triethylamine as a reaction catalyst were uniformly After dissolving in a solvent, 270 parts by weight of acrylic acid was added dropwise under reflux for 2 hours, and then air was blown and stirred under reflux at 110 ° C for 5 hours. In order to adsorb In the ionic impurities in the solution, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (manufactured by Hoffmann Mineral Co., Ltd., Sillitin V85) to obtain a 50% partial acrylic acid modification. Bisphenol A type epoxy resin (H).

(Synthesis Example C) Inclusion of acrylic acid modified diphenyl ether type epoxy resin (C)

1000 parts by weight of a diphenyl ether type epoxy resin (YSLV-80DE, manufactured by Nippon Steel Chemical Co., Ltd.), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and 2 parts by weight of triethylamine as a reaction catalyst. Further, 234 parts by weight of acrylic acid was stirred under reflux at 90 ° C while blowing air, and the reaction was carried out for 6 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (Sillitin V85, manufactured by Hoffmann Mineral Co., Ltd.) to obtain 50% of the resin. Acrylic modified diphenyl ether type epoxy resin (C).

(Synthesis Example D) Synthesis of methacrylic acid modified bisphenol E type epoxy resin (D)

163 parts by weight of bisphenol E type epoxy resin R-1710 (manufactured by Printec Co., Ltd.) was dissolved in a solvent, and 0.5 parts by weight of p-methoxyphenol as a polymerization inhibitor was used as a reaction catalyst. 0.5 parts by weight of the amine and 40 parts by weight of methacrylic acid were refluxed while being blown at 90 ° C for 5 hours to carry out a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (Sillitin V85, manufactured by Hoffmann Mineral Co., Ltd.) to obtain 50% of the resin. A methacrylic acid modified bisphenol E type epoxy resin (curable resin D).

(Synthesis Example E) Synthesis of Acrylic Modified Phenol Novolak Epoxy Resin (E)

1100 parts by weight of a liquid phenol novolak type epoxy resin (manufactured by Dow Chemical Co., Ltd.: DEN431), 2.2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and 2.2 parts by weight of triethylamine as a reaction catalyst. Further, 220 parts by weight of acrylic acid was stirred under reflux at 90 ° C while blowing air, and the reaction was carried out for 5 hours. In order to adsorb ionic impurities in the reactants, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (manufactured by Hoffmann Mineral Co., Ltd., Sillitin V85) to obtain an acrylic modified phenol novolak epoxy resin (E) ( 50% partial acrylate).

(Synthesis Example F) Synthesis of Amine Ester-modified Acrylic Epoxy Resin (F)

1100 parts by weight of trimethylolpropane, 1.6 parts by weight of 3,5-dibutyl-4-hydroxytoluene as a polymerization inhibitor, 0.08 parts by weight of dibutyltin dilaurate as a reaction catalyst, and isophorone 5400 parts by weight of diisocyanate was stirred under reflux at 60 ° C and reacted for 2 hours. Then, 210 parts by weight of 2-hydroxyethyl acrylate and 910 parts by weight of glycidol were added, and the mixture was refluxed and stirred at 90 ° C for 2 hours while blowing air. Then, in order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (Sillitin V85, manufactured by Hoffmann Mineral Co., Ltd.) to obtain an amine. Ester-modified acrylic epoxy resin (F).

(Synthesis Example G) Synthesis of Amine Ester Modified Methyl Acrylate Epoxy Resin (G)

1100 parts by weight of trimethylolpropane, 1.6 parts by weight of 3,5-dibutyl-4-hydroxytoluene as a polymerization inhibitor, 0.08 parts by weight of dibutyltin dilaurate as a reaction catalyst, and diphenylmethane 6080 parts by weight of diisocyanate was stirred under reflux at 60 ° C and reacted for 2 hours. Then, 235 parts by weight of 2-hydroxyethyl methacrylate and 910 parts by weight of glycidol were added, and the mixture was refluxed while stirring at 90 ° C for 2 hours while blowing air. Then, in order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained resin was filtered using a column packed with a natural combination of crystal and kaolin (Sillitin V85, manufactured by Hoffmann Mineral Co., Ltd.) to obtain an amine. Ester modified methacrylic epoxy resin (G).

[Manufacture of sealant]

Sealant (1)

85 parts by weight of acrylic acid modified resorcinol type epoxy resin (A), 18 parts by weight of acrylic acid modified bisphenol A type epoxy resin (B), and acrylic modified diphenyl ether type by a planetary stirring device 33 parts by weight of epoxy resin (C), 10 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one as a photoradical polymerization initiator, as a latent heat hardener 38 parts by weight of a hardening agent (Amicure VDH, Ajinomoto Fine-Techno Co., Ltd.), 6 parts by weight of γ-glycidoxypropyltrimethoxydecane, and spherical cerium oxide (SO-C1 manufactured by Admatechs Co., Ltd.) 30 parts by weight and 20 parts by weight of core-shell fine particles (manufactured by Japan Zeon Co., Ltd.: F-351) were mixed and stirred so as to be a uniform liquid, and then mixed by a ceramic three-roller and further processed by a planetary stirring device. Defoaming, mixing and stirring, and making it into a sealant (1). The properties of the obtained sealant (1) are shown below.

Hydrogen bond functional group value: 4.8 × 10 ^-3

Specific resistance of the sealant before hardening (Ω‧cm): 7.2×10 ⁹

Volume resistivity of the sealant after hardening (Ω‧cm): 2.6×10 ¹³

Sealant (2)

100 parts by weight of a phenol novolac type epoxy resin ("N-740", manufactured by DIC Corporation) and 60 parts by weight of a methacrylic acid modified bisphenol E type epoxy resin (D) as a light by a planetary stirring device 3 parts by weight of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one as a latent thermosetting initiator 65 parts by weight of an antimony-based hardener (Amicure VDH, Ajinomoto Fine-Techno Co., Ltd.), 3 parts by weight of γ-glycidoxypropyltrimethoxydecane, 6 parts by weight of talc, and dibutyl as an antioxidant. 0.5 parts by weight of the hydroxytoluene was mixed and stirred so as to be a homogeneous liquid, and then mixed by a ceramic three-roller, and further defoamed and mixed and stirred by a planetary stirring device to obtain a sealant (2). The properties of the obtained sealant (2) are shown below.

Hydrogen bond functional group value: 3.7 × 10 ^-3

Specific resistance of sealant before hardening (Ω‧cm): 2.4×10 ⁷

Volume resistivity of the sealant after hardening (Ω‧cm): 1.3×10 ¹³

Sealant (3)

60 parts by weight of an acrylic modified phenol novolak epoxy resin (E), 29 parts by weight of an amine ester modified acrylic epoxy resin (F), 2,2-diethoxybenzene as a photopolymerization initiator 1.5 parts by weight of a ketone, 22 parts by weight of an oxime-based curing agent (Amicure VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 1.5 parts by weight of γ-glycidoxypropyltrimethoxydecane, and 2 34 parts by weight of cerium oxide particles (average particle diameter: 1.5 μm), and stirred by a planetary stirring device, and then mixed by a ceramic three-roller, and further defoamed and mixed by a planetary stirring device to prepare a cerium oxide particle. Sealant (3). The properties of the obtained sealant (3) are shown below.

Hydrogen bond functional group value: 4.3 × 10 ^-3

Specific resistance of sealant before hardening (Ω‧cm): 2.1×10 ⁹

Volume resistivity of the sealant after hardening (Ω‧cm): 1.8×10 ¹³

Sealant (4)

35 parts by weight of a modified bisphenol A type epoxy resin (B) as a curable resin, and 30 parts by weight of a caprolactone-modified bisphenol A type epoxy acrylate ("Ebecryl 3708" manufactured by Daicel Cytec Co., Ltd.) And 2,2-dimethoxy-2-phenylbenzene mixed with 25 parts by weight of an acrylic modified bisphenol F type epoxy resin (manufactured by Daicel Cytec Co., Ltd., KRM8287), and further blended into a photopolymerization initiator 2 parts by weight of ethyl ketone, 6 parts by weight of bismuth sebacate ("SDH" manufactured by Otsuka Chemical Co., Ltd.) as a thermal curing agent, and 25 parts by weight of cerium oxide (SO-C1 manufactured by Admatechs Co., Ltd.) as a filler. 2 parts by weight of γ-glycidoxypropyltrimethoxydecane ("KBM-403", manufactured by Shin-Etsu Silicones Co., Ltd.) as a decane coupling agent, and core-shell acrylate copolymer fine particles (manufactured by Ganz Chemical Co., Ltd., F351) 17 parts by weight, the mixture was stirred by a planetary stirring device, and then mixed by a ceramic three-roller, and further defoamed and mixed and stirred by a planetary stirring device to prepare a sealant (4). The properties of the obtained sealant (4) are shown below.

Hydrogen bond functional group value: 4.1 × 10 ^-3

Specific resistance of sealant before hardening (Ω‧cm): 8.9×10 ⁸

Volume resistivity of the sealant after hardening ‧ (Ω ‧ cm): 1.7 × 10 ¹³

Sealant (5)

50 parts by weight of a methacrylic acid modified bisphenol E type epoxy resin (D), 50 parts by weight of an amine ester modified methacrylic epoxy resin (G), and 2, 2 - 2 as a photopolymerization initiator 1.5 parts by weight of ethoxyacetophenone, 18 parts by weight of lanthanum hardener (Amicure VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.) as a latent heat curing agent, γ-glycidoxypropyltrimethoxydecane 1.5 35 parts by weight of bismuth dioxide particles (SO-C1, manufactured by Admatech Co., Ltd.), stirred by a planetary stirring device, mixed by a ceramic three-roller, and defoamed and mixed by a planetary stirring device. And made it into a sealant (5). The properties of the obtained sealant (5) are shown below.

Hydrogen bond functional group value: 3.6 × 10 ^-3

Specific resistance of sealant before hardening (Ω‧cm): 4.1×10 ⁶

Volume resistivity of the sealant after hardening (Ω‧cm): 1.1×10 ¹³

Comparative sealant (C1)

The blending is composed of 35 parts by weight of urethane acrylate (AH-600 manufactured by Kyoeisha Chemical Co., Ltd.), 15 parts by weight of 2-hydroxybutyl acrylate, 50 parts by weight of isodecyl acrylate, and 3 parts by weight of benzophenone. The curable resin composition was stirred by a planetary stirring device, and then uniformly mixed by a ceramic three-roller to obtain a photocurable comparative sealant (C1). The characteristics of the comparative sealant (C1) obtained are shown below.

Hydrogen bond functional group value: 2.2 × 10 ^-5

Specific resistance of sealant before hardening (Ω‧cm): 6.0×10 ⁵

Volume resistivity of the sealant after hardening (Ω‧cm): 1.2×10 ¹³

Compare sealant (C2)

Blending 50 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828US), 25 parts by weight of a curable resin composition composed of a lanthanum hardener (manufactured by JAPAN HYDRAZINE Co., Ltd., NDH), which was stirred by a planetary stirring device, and then uniformly mixed by a ceramic three-roller to obtain a comparative sealant (C2) ). The characteristics of the comparative sealant (C2) obtained are shown below.

Hydrogen bond functional group 価: 2.7×10 ^-7

Specific resistance of sealant before hardening (Ω‧cm): 5.0×10 ¹⁰

Volume resistivity of the sealant after hardening (Ω‧cm): 3.0×10 ¹³

(Examples 1 to 5)

A transparent electrode is formed on the first substrate, a black matrix (BM) is formed on the second substrate, and a horizontal alignment alignment film (AL-1051) is formed on the opposite side of each substrate, and then alignment treatment is performed. The sealants (1) to (5) are filled in a syringe for dispensing, and after defoaming treatment, each sealant is applied to the alignment film of the first substrate by using a dispenser to draw a rectangular frame. side. The microdroplet of the following liquid crystal composition 1 was applied to the entire surface of the first substrate in a state where the sealant was not cured, and the vacuum bonding apparatus was used immediately to bond the second substrate under a vacuum of 5 Pa. . After the vacuum was released, the line width of the sealant which was crushed was about 1.2 mm, and the drawing conditions and the gap between the substrates were adjusted so that 0.3 mm and BM overlapped. Immediately using a high-pressure mercury lamp, ultraviolet rays were irradiated to the sealing portion at 100 mW/cm ^{2 for} 30 seconds from the second substrate side, and thereafter, liquid crystal annealing was performed at 120 ° C for 1 hour to thermally harden, and the IPS method of Examples 1 to 5 was produced. Liquid crystal display device (d _gap = 4.0 μm). The physical property values of the liquid crystal composition 1 are shown in Table 2. The VHR of the obtained liquid crystal display device was measured. Moreover, the alignment unevenness and the afterimage evaluation of the obtained liquid crystal display device were performed. The results are shown in Table 3.

It is understood that the liquid crystal composition 1 has a liquid crystal layer temperature range of 75.8 ° C which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has a low viscosity and an optimum Δn.

The liquid crystal display devices of Examples 1 to 5 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 6 to 15)

Liquid crystal compositions 2 to 3 shown in Table 4 were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 6 to 15 were produced using the sealants (1) to (5), and VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 5 to 6.

It is understood that the liquid crystal compositions 2 and 3 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have a low viscosity and an optimum Δn.

The liquid crystal display devices of Examples 6 to 15 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 16 to 30)

Liquid crystal compositions 4 to 6 shown in Table 7 were sandwiched in the same manner as in Example 1, and liquid crystal display devices of Examples 16 to 30 were produced using the sealants (1) to (5), and VHR and ID were measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 8 to 10.

It is understood that the liquid crystal compositions 4 to 6 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have a low viscosity and an optimum Δn.

The liquid crystal display devices of Examples 16 to 30 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 31 to 45)

A transparent electrode is formed on the first and second substrates, a black matrix (BM) is formed on the second substrate, and a horizontal alignment alignment film (SE-7492) is formed on the opposite side of each substrate, and then subjected to alignment treatment. In the same manner as in the first embodiment, the liquid crystal compositions 7 to 9 shown in Table 11 were sandwiched, and the TN liquid crystal display devices of Examples 31 to 45 were produced using the sealants (1) to (5) (d _gap = 3.5 μm). , determine its VHR and ID. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 12 to 14.

The liquid crystal compositions 7 to 9 have a practical liquid crystal layer temperature range as a liquid crystal composition for TV, have a large absolute value of dielectric anisotropy, and have a low viscosity and an optimum Δn.

The liquid crystal display devices of Examples 31 to 45 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 46 to 55)

A transparent electrode is formed on the first substrate, a black matrix (BM) is formed on the second substrate, and a horizontal alignment alignment film (AL-1051) is formed on the opposite side of each substrate, and then alignment treatment is performed. In the same manner as in the first embodiment, the liquid crystal compositions 10 to 11 shown in Table 15 were sandwiched, and the FFS-type liquid crystal display devices of Examples 46 to 55 were produced using the sealants (1) to (5) (d _gap = 4.0 μm). , determine its VHR and ID. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 16 to 17.

The liquid crystal compositions 10 to 11 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum. △n.

The liquid crystal display devices of Examples 46 to 55 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 56 to 65)

In the same manner as in Example 46, the liquid crystal compositions 12 to 13 shown in Table 18 were sandwiched, and the liquid crystal display devices of Examples 56 to 65 were produced using the sealants (1) to (5), and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 19 to 20.

The liquid crystal compositions 12 to 13 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have a low viscosity and an optimum Δn.

The liquid crystal display devices of Examples 56 to 65 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 66 to 70)

In the liquid crystal composition 10 used in Example 46, 0.3% by mass of bis(methacrylic acid)biphenyl-4,4'-diester was mixed to prepare a liquid crystal composition 14, and the liquid crystal composition was sandwiched in the same manner as in Example 31. 14. Seal with sealant (1)~(5). A liquid crystal display device of TN type of Examples 66 to 70 was produced by directly irradiating ultraviolet rays for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Table 21.

The liquid crystal display devices of Examples 66 to 70 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 71 to 75)

In the liquid crystal composition 8 used in Example 36, 0.3% by mass of bis(methacrylic acid)biphenyl-4,4'-diester was mixed to prepare a liquid crystal composition 15, and the liquid crystal composition was sandwiched in the same manner as in Example 1. 15, sealed with sealant (1) ~ (5). The IPS liquid crystal display device of Examples 71 to 75 was produced by directly irradiating ultraviolet rays for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Table 22.

The liquid crystal display devices of Examples 71 to 75 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Examples 76 to 80)

In the liquid crystal composition 6 used in Example 26, 0.3% by mass of 3-fluorobiphenyl-4,4'-diester of bis(methacrylic acid) was mixed to prepare a liquid crystal composition 16, and the liquid crystal composition 16 was sandwiched in the same manner as in Example 46. The liquid crystal composition 16 is sealed with a sealant (1) to (5). A liquid crystal display device of the FFS type of Examples 76 to 80 was produced by directly irradiating ultraviolet rays for 600 seconds (3.0 J/cm ² ) in a state where a driving voltage was applied between the electrodes, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Table 23.

The liquid crystal display devices of Examples 76 to 80 can achieve a higher VHR. Further, in the evaluation of the alignment unevenness, there is no unevenness in alignment, or even if there is little, it is an allowable level. Furthermore, there is no residual image in the evaluation of the afterimage, or even if there are few, it is an allowable level.

(Comparative examples 1 to 5)

In the first embodiment, the IPS liquid crystal display devices of Comparative Examples 1 to 5 were produced in the same manner except that the liquid crystal composition 1 was changed to the comparative liquid crystal composition 1 shown below, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Table 25.

In the liquid crystal display devices of Comparative Examples 1 to 5, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

(Comparative examples 16 to 15)

An IPS liquid crystal display device of Comparative Examples 6 to 15 was produced in the same manner as in Comparative Example 1, except that the liquid crystal composition 1 was changed to the comparative liquid crystal compositions 2 and 3 shown below, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 27-28.

In the liquid crystal display devices of Comparative Examples 6 to 15, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

(Comparative examples 16 to 25)

An IPS liquid crystal display device of Comparative Examples 16 to 25 was produced in the same manner as in Comparative Example 1, except that the liquid crystal composition 1 was changed to the comparative liquid crystal compositions 4 and 5 shown below, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 30 to 31.

In the liquid crystal display devices of Comparative Examples 16 to 25, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

(Comparative examples 26 to 40)

An IPS liquid crystal display device of Comparative Examples 26 to 40 was produced in the same manner as in Comparative Example 1, except that the liquid crystal composition 1 was changed to the comparative liquid crystal compositions 6 to 8, and the VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 33 to 35.

In the liquid crystal display devices of Comparative Examples 26 to 40, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

(Comparative Examples 41 to 55)

An IPS liquid crystal display device of Comparative Examples 41 to 55 was produced in the same manner as in Comparative Example 1, except that the liquid crystal composition 1 was changed to the comparative liquid crystal compositions 9 to 11. The VHR was measured. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 37 to 39.

In the liquid crystal display devices of Comparative Examples 41 to 55, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

(Comparative Examples 56 to 71)

Comparative Examples 56 to 71 were produced in the same manner except that the sealants were changed to the comparative sealants (C1) and (C2) in Examples 5, 13, 17, 25, 37, 45, 61 and 65. The liquid crystal display device measures its VHR. Further, the alignment unevenness evaluation and the afterimage evaluation of the liquid crystal display device were performed. The results are shown in Tables 40 to 43.

In the liquid crystal display devices of Comparative Examples 56 to 71, the VHR was lower than that of the liquid crystal display device of the present invention. Further, in the evaluation of the alignment unevenness, the occurrence of the uneven distribution was also confirmed and it was not acceptable. Further, in the evaluation of the afterimage, the occurrence of the afterimage was also confirmed and it was not acceptable.

Claims (13)

A liquid crystal display device comprising: a first substrate and a second substrate; and a liquid crystal layer containing a liquid crystal composition sandwiched between the first substrate and the second substrate, wherein the first substrate and the second substrate pass through an energy line or a cured product of a heat-hardened curable resin composition containing one or two or more compounds represented by the formula (I). (wherein R ³¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and M ³¹ to M ³³ are independently represented by trans-1,4- Cyclohexyl or 1,4-phenylene, one or two -CH ₂ - of the trans-1,4-cyclohexylene group can also be substituted by -O- in such a manner that the oxygen atoms are not directly adjacent to each other. One or two hydrogen atoms in the phenylene group may be substituted by a fluorine atom, X ³¹ and X ³² independently represent a hydrogen atom or a fluorine atom, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group. , n ³¹ and n ³² represent 0, 1 or 2 independently of each other, n ³¹ + n ³² represents 0, 1 or 2, and M ³¹ and M ³³ may be the same or different when there are a plurality of cases, and contain 1 Or a compound selected from the group consisting of compounds represented by the general formula (II-b) to the general formula (II-f), (wherein R ²¹ to R ³⁰ independently of each other represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ²¹ represents a hydrogen atom or fluorine. (Atom), the curable resin composition contains a compound having at least one (meth)acrylic group and an epoxy group in one molecule, and the hardening functional group of the curable resin composition has a hydrogen bond functional value of 3 × 10 ^{- 3} ~ 5 × 10 ^-3 mol / g. The liquid crystal display device of claim 1, wherein the curable resin composition contains a polymerization initiator. The liquid crystal display device of claim 2, wherein the polymerization initiator is a photopolymerization initiator and/or a thermal polymerization initiator. The liquid crystal display device according to any one of claims 1 to 3, wherein the curable resin composition contains a decane coupling agent. The liquid crystal display device according to any one of claims 1 to 3, wherein the curable resin composition contains a filler. The liquid crystal display device according to any one of claims 1 to 3, wherein the compound having at least one (meth)acrylic group and an epoxy group in each of the molecules is modified by (meth)acrylic acid. Epoxy resin and / or urethane modified (meth) acrylic epoxy resin. The liquid crystal display device according to any one of claims 1 to 3, wherein the curable resin composition contains a resin having a (meth)acryloxy group and/or a resin having an epoxy group. The liquid crystal display device according to any one of claims 1 to 3, wherein the equivalent ratio of the (meth)acrylic group to the epoxy group of the curable resin composition is from 40:60 to 95:5. The liquid crystal display device according to any one of claims 1 to 3, wherein the curable resin composition contains resin fine particles. The liquid crystal display device according to any one of claims 1 to 3, wherein the compound represented by the formula (I) is a compound represented by the formula (Ia) to the formula (If), (wherein R ³² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms, X ³¹ to X ³⁸ represent a hydrogen atom or a fluorine atom independently of each other, and Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group). The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer further contains one or more selected from the group consisting of the formula (III-a) to the formula (III-). f) a compound expressed in the group of compounds, (wherein R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms, X ⁴¹ to X ⁴⁸ represent a hydrogen atom or a fluorine atom independently of each other, and Z ⁴¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group). The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer is composed of a polymer containing one or more types of polymerizable compounds. The liquid crystal composition of the substance is polymerized, and the polymerizable compound has a liquid crystal skeleton in which a plurality of six-membered rings are connected. The liquid crystal display device according to any one of claims 1 to 3, wherein the liquid crystal composition layer contains a difunctional monomer represented by the general formula (V), (wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH _{2 ) s} - (wherein, s represents an integer from 2 to 7, such that the oxygen atom is bonded to the aromatic ring), and Z ¹ represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, - CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO -CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -,- OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C - or a single bond, C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any hydrogen atom of all 1,4-phenylene groups in the formula may be substituted by a fluorine atom. ).