WO2023120683A1

WO2023120683A1 - Sealing agent for liquid crystal display elements, liquid crystal display element and polyvalent hydrazide compound

Info

Publication number: WO2023120683A1
Application number: PCT/JP2022/047508
Authority: WO
Inventors: 勇人 ▲高▼田; 達也草加; 唯一洲上; 大輝山脇; ▲高▼岡恵理奈山野; 大輔柴田; さやか脇岡
Original assignee: 積水化学工業株式会社
Priority date: 2021-12-24
Filing date: 2022-12-23
Publication date: 2023-06-29
Also published as: JP2024020438A; TW202336205A; JP7389304B2; JPWO2023120683A1

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal display elements, the sealing agent being excellent in terms of storage stability, adhesive properties, and low liquid crystal contamination properties. Another purpose of the present invention is to provide: a liquid crystal display element which is obtained using the above-described sealing agent for liquid crystal display elements; and a polyvalent hydrazide compound which can be used for the above-described sealing agent for liquid crystal display elements. The present invention provides a sealing agent for liquid crystal display elements, the sealing agent containing a curable resin and a thermal curing agent, wherein the thermal curing agent contains a compound which has primary amino groups and/or hydrazide groups in each molecule, with the number of the groups being 2 or more in total, while having at least either a sulfonyl group bonded to an aromatic ring or a carbonyl group bonded to an aromatic ring.

Description

Sealant for liquid crystal display element, liquid crystal display element, and polyvalent hydrazide compound

The present invention relates to a sealant for liquid crystal display elements. The present invention also relates to a liquid crystal display element using the sealing agent for liquid crystal display elements, and a polyhydric hydrazide compound that can be used for the sealing agent for liquid crystal display elements.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, dropping using a sealing agent as disclosed in Patent Document 1 and Patent Document 2 A liquid crystal dropping method called construction method is used.
In the dropping method, first, a frame-shaped seal pattern is formed on one of the two electrode-attached substrates by dispensing. Next, liquid crystal microdroplets are dropped into the frame of the seal pattern while the sealant is not yet cured, and the other substrate is superimposed under vacuum, and the sealant is cured to fabricate a liquid crystal display element. At present, this dripping method is the mainstream method for manufacturing liquid crystal display elements.

By the way, in the present age when various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widely used, miniaturization of devices is the most demanded issue. As a method for downsizing the device, narrowing the frame of the liquid crystal display part is mentioned, and for example, the position of the seal part is arranged under the black matrix (hereinafter also referred to as narrow frame design).

JP-A-2001-133794 WO 02/092718 Japanese Patent No. 3053499 Japanese Patent No. 5796890 Japanese Patent No. 4974344

Since the sealant is also placed on the alignment film in the narrow frame design, there is a demand for a sealant for liquid crystal display elements that is excellent in adhesion not only to the substrate but also to the alignment film. Such a sealing agent for liquid crystal display elements expresses high adhesive strength by photocuring and thermal curing, and as a method of thermal curing, a thermosetting agent is blended into the sealing agent for liquid crystal display elements. there is However, when a thermosetting agent having a low reaction initiation temperature is used to improve the curability and adhesiveness of the liquid crystal display element sealing agent, the obtained liquid crystal display element sealing agent has poor storage stability. was there. Moreover, when a thermosetting agent having a high reaction initiation temperature is used, the obtained sealing compound for liquid crystal display elements may be inferior in liquid crystal contamination resistance. In the future, if the frame becomes narrower or the liquid crystal material is changed, there is a risk that liquid crystal contamination will occur due to the uncured sealant component eluting into the liquid crystal, even if the sealant has no problems in the past. There is Therefore, there has been a demand for a sealant that is more excellent in reducing liquid crystal contamination.

Hydrazide compounds are often used as curing agents and cross-linking agents for epoxy resins and acrylic resins in the fields of paints and adhesives. Hydrazide compounds are highly reactive and thus can be cured at low temperature. Moreover, they have high crystallinity and excellent storage stability. Therefore, they are suitable as a curing agent or a cross-linking agent in a one-component curable resin composition. Used. However, conventional hydrazide compounds have insufficient heat resistance, and are difficult to apply to electronic materials and vehicle-mounted materials that require heat resistance. Therefore, for example, Patent Literature 3 discloses a hydrazide compound with improved heat resistance, but when such a hydrazide compound is used in a curable resin composition, storage stability and adhesiveness are deteriorated. However, it was difficult to achieve both.

On the other hand, in recent years, liquid crystal display elements and organic EL display elements have been widely used as display elements having features such as thinness, light weight, and low power consumption. In such display elements and other electronic devices, adhesives for electronic materials and sealants for liquid crystal display elements are usually used for adhesion of various members, sealing of liquid crystals and light-emitting layers, and the like. Hydrazide compounds are sometimes used as curing agents or cross-linking agents for adhesives for electronic materials and sealants for liquid crystal display elements because of their excellent storage stability and low-temperature curability (for example, Patent Documents 4 and 5). ), and problems such as liquid crystal contamination.

An object of the present invention is to provide a sealant for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. Another object of the present invention is to provide a liquid crystal display element using the sealing agent for a liquid crystal display element, and a polyhydric hydrazide compound that can be used for the sealing agent for the liquid crystal display element.

The present disclosure 1 is a sealant for a liquid crystal display element containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains at least one of a primary amino group and a hydrazide group in one molecule. The sealant for a liquid crystal display element contains a compound having two or more and having at least one of a sulfonyl group bonded to an aromatic ring and a carbonyl group bonded to an aromatic ring.
The present disclosure 2 is that the thermosetting agent has a total of two or more primary amino groups and hydrazide groups in one molecule, and the following formula (1-1) and the following formula (1-2) ).
The present disclosure 3 is that the thermosetting agent has two or more primary amino groups in one molecule and has at least one structure of the above formula (1-1) and the above formula (1-2). It is a sealant for a liquid crystal display element of the present disclosure 2 containing a compound having.
The present disclosure 4 includes a compound in which the thermosetting agent has a total of two or more primary amino groups and/or hydrazide groups in one molecule and has the structure of formula (1-2). It is a sealant for a liquid crystal display element of the present disclosure 2.
The present disclosure 5 is the sealant for a liquid crystal display element of the present disclosure 4, wherein the thermosetting agent contains a compound having two or more hydrazide groups in one molecule and having the structure of the formula (1-2). be.
The present disclosure 6 is that the thermosetting agent has two or more primary amino groups in one molecule, and has the following formulas (2-1), (2-2), (2-3), or A sealant for a liquid crystal display element according to the present disclosure 1, which contains a compound having a structure represented by (2-4).
The present disclosure 7 has two or more primary amino groups in one molecule, and the above formula (2-1), (2-2), (2-3), or (2-4) The compound having the structure represented by the following formula (3-1), (3-2), or the sealant for a liquid crystal display element of the present disclosure 6 having a structure represented by (3-3) .
The present disclosure 8 has two or more primary amino groups in one molecule, and the above formula (2-1), (2-2), (2-3), or (2-4) A compound having a structure represented by the following formulas (4-1), (4-2), (4-3), (4-4), (4-5), or (4-6) It is a sealant for a liquid crystal display element of the present disclosure 7, which is the compound represented.
The present disclosure 9 is that the thermosetting agent includes a polyvalent hydrazide compound having two or more hydrazide groups represented by the following formula (5) in one molecule and having a sulfonyl group bonded to an aromatic ring. It is a sealant for a liquid crystal display element of Disclosure 1.
The present disclosure 10 is the sealant for a liquid crystal display element according to the present disclosure 9, wherein the polyhydrazide compound has a structure represented by the following formula (6).
Present Disclosure 11 is the sealant for a liquid crystal display element according to Present Disclosure 10, wherein at least one of R ¹ to R ⁴ in the structure represented by the above formula (6) contains an amino group or a hydroxyl group.
The present disclosure 12 is a sealant for a liquid crystal display element containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains at least one of a primary amino group and a hydrazide group in one molecule. 2 or more, and among the constituent atoms, the average charge is 0.4a. u. It is a sealant for liquid crystal display elements containing a compound having atoms as large as above.
13 of the present disclosure is the sealant for a liquid crystal display element according to 12 of the present disclosure, wherein the thermosetting agent has a reaction initiation temperature with bisphenol F diglycidyl ether of 120° C. or higher.
The present disclosure 14 is the liquid crystal display element sealant according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the curable resin contains an epoxy compound. be.
The present disclosure 15 is the liquid crystal display of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein the curable resin contains a (meth)acrylic compound. It is a sealant for devices.
The present disclosure 16 further includes the liquid crystal display element of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 containing a photopolymerization initiator It is a sealant.
This disclosure 17 is the liquid crystal of this disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, further containing a thermal radical polymerization initiator. It is a sealant for display elements.
The present disclosure 18 is present disclosures 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11, wherein the 10% weight loss temperature after curing of the sealant for a liquid crystal display element is 350°C or higher. , 12, 13, 14, 15, 16 or 17.
The present disclosure 19 is the liquid crystal display element sealant of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 It is a liquid crystal display element having a cured product.
The present disclosure 20 is a polyvalent hydrazide compound having two or more hydrazide groups represented by the following formula (5) in one molecule and having a sulfonyl group bonded to an aromatic ring.
The present disclosure 21 is a polyhydric hydrazide compound of the present disclosure 20 having a structure represented by formula (6) below.
The present disclosure 22 is the multivalent hydrazide compound of the present disclosure 21, wherein at least one of R ¹ to R ⁴ in the structure represented by the above formula (6) contains an amino group or a hydroxyl group.

In formulas (1-1) and (1-2), * represents a bonding position.

In formulas (2-1) to (2-4), * represents a bonding position.

In formulas (3-1) to (3-3), * represents a bonding position.

In formula (5), * represents a binding position.

In formula (6), R ¹ to R ⁴ are each independently a group containing at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a nitrogen atom, a hydrogen atom, or , represents a linking group, and at least one of R ¹ to R ⁴ is bonded to the hydrazide group represented by the above formula (5).

The present invention will be described in detail below.
Hereinafter, the liquid crystal display element sealing compound of the present disclosure 1 is also referred to as "the liquid crystal display element sealing compound of the present invention 1". Further, the sealant for liquid crystal display elements of the present disclosure 2 is also referred to as "the sealant for liquid crystal display elements of the first aspect of the present invention", and the sealant for liquid crystal display elements of the present disclosure 6 is referred to as the "liquid crystal display of the first aspect of the present invention. The liquid crystal display element sealing compound of the present disclosure 9 is also referred to as the "liquid crystal display element sealing compound of the first aspect 3 of the present invention". Further, the liquid crystal display element sealing compound of the present disclosure 12 is also referred to as "the liquid crystal display element sealing compound of the present invention 2". In addition, the polyhydrazide compound of the present disclosure 20 is also referred to as "the polyhydrazide compound of the present invention".
Regarding items common to the sealing compound for liquid crystal display elements of Invention 1 (including aspects 1 to 3) and the sealing compound for liquid crystal display elements of Invention 2, refer to "Sealant for liquid crystal display elements of the present invention". described as

As a thermosetting agent, the present inventors have found that at least one of primary amino groups and hydrazide groups is present in total in one molecule, and a sulfonyl group bonded to an aromatic ring and a carbonyl bonded to an aromatic ring We considered using compounds having at least one of the groups. As a result, the present inventors have found that a sealant for liquid crystal display elements which is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination can be obtained, and have completed the present invention 1.
In addition, the present inventors have found that the thermosetting agent has a total of two or more primary amino groups and/or hydrazide groups in one molecule, and that the constituent atoms have an average charge inherent to the atom. We considered using a compound having an atom that is greater than the charge by a specific value or more. As a result, the present inventors have found that a sealant for liquid crystal display elements that is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination can be obtained, and have completed Invention 2.
Further, the polyhydrazide compound of the present invention and the curable resin composition containing the polyhydrazide compound can be suitably used for adhesives for electronic materials and sealants for liquid crystal display elements, and particularly for liquid crystal display elements. When used as a sealant, a liquid crystal display element with little liquid crystal contamination and excellent long-term reliability can be obtained.

The sealant for liquid crystal display elements of the present invention contains a thermosetting agent.
In the liquid crystal display element sealant of the present invention 1, the thermosetting agent has a total of two or more primary amino groups or hydrazide groups in one molecule, and a sulfonyl group bonded to an aromatic ring. and a compound having at least one of a carbonyl group bonded to an aromatic ring (hereinafter also referred to as "thermosetting agent according to the first invention").

The thermosetting agent according to the present invention 1 has a total of two or more of at least one of primary amino groups and hydrazide groups in one molecule. Since the thermosetting agent according to the present invention 1 has a total of two or more of at least one of primary amino groups and hydrazide groups in one molecule, the sealing agent for a liquid crystal display element of the present invention 1 has curability and adhesiveness. It will be excellent in quality.

The thermosetting agent according to the present invention 1 has at least one of a sulfonyl group bonded to an aromatic ring and a carbonyl group bonded to an aromatic ring. Among others, the thermosetting agent according to the first aspect of the invention preferably has a sulfonyl group bonded to the aromatic ring.

In the thermosetting agent according to the present invention 1, examples of the aromatic ring bonded to the sulfonyl group or carbonyl group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring and the like. In addition, the aromatic ring may contain heteroatoms such as oxygen, nitrogen, sulfur and phosphorus. Among them, a benzene ring is preferred.

The sealant for a liquid crystal display element according to Embodiment 1 of the present invention has, as the thermosetting agent according to the present invention 1, a total of two or more of at least one of primary amino groups and hydrazide groups in one molecule, and It includes a compound having at least one of the structures of formula (1-1) and formula (1-2) (hereinafter also referred to as "thermosetting agent according to aspect 1 of the present invention"). The thermosetting agent according to aspect 1 of the present invention has a structure of at least one of the above formula (1-1) and the above formula (1-2), whereby the sealant for a liquid crystal display element of the first aspect 1 of the present invention is excellent in storage stability and low liquid crystal contamination.

The thermosetting agent according to aspect 1 of the present invention has two or more primary amino groups in one molecule, and at least one of the above formula (1-1) and the above formula (1-2) Compounds with structures are preferred. Further, the thermosetting agent according to the first aspect of the present invention has at least two or more primary amino groups or hydrazide groups in total in one molecule, and has the structure of the above formula (1-2). A compound having two or more hydrazide groups in one molecule and having the structure of the above formula (1-2) is more preferable.

The thermosetting agent according to aspect 1 of the present invention has an average charge of 0.4 a. u. It is preferable to have atoms larger than . The thermosetting agent according to aspect 1 of the present invention has an average charge of 0.4 a. u. By having atoms as large as above, the sealant for a liquid crystal display element of the first aspect of the present invention is excellent in storage stability and low liquid crystal contamination. The thermosetting agent according to aspect 1 of the first aspect of the present invention has an average charge of 0.6 a. u. It is more preferred to have atoms larger than 0.65 a. u. It is even more preferred to have atoms that are larger than or equal to.
In addition, the above "a.u." means an atomic unit, and 1a.u. u. is 1.60217653×10 ⁻¹⁹ C.
Also, the average atomic charge can be derived using GAMESS (US) from Iowa State University (the same applies to the thermosetting agent according to the present invention 2, which will be described later). Specifically, the target molecule is modeled, and after the structural optimization calculation by B3LYP/6-31G(d, p), the RESP charge of the entire molecule is calculated under the same conditions, and the charges of the corresponding atoms are averaged. can be derived by In addition, the theoretical charge peculiar to the atom is calculated using calculation software such as GAMESS (US), Gaussian, Firefly, etc., and the structure optimization calculation of the target molecule and the calculation of the RESP charge are performed by B3LYP / 6-31G (d, p). It is a value indicated by calculation.

The preferable lower limit of the reaction initiation temperature of the thermosetting agent according to the first aspect of the present invention with bisphenol F diglycidyl ether is 120°C. When the reaction initiation temperature is 120° C. or higher, the obtained sealing agent for liquid crystal display elements has excellent storage stability. A more preferable lower limit of the reaction initiation temperature is 130°C, and a further preferable lower limit is 135°C.
From the viewpoint of curability of the obtained sealing agent for liquid crystal display elements, the upper limit of the reaction initiation temperature is preferably 220°C, more preferably 215°C, and still more preferably 210°C.
The temperature at which the thermosetting agent starts to react with bisphenol F diglycidyl ether can be measured by the following method (the same applies to the thermosetting agent according to the present invention 2, which will be described later).
That is, first, 10 g of a heat curing agent and 100 g of bisphenol F diglycidyl ether are stirred for 1 minute at a stirring speed of 2000 rpm using a planetary stirrer (manufactured by THINKY Co., Ltd., "Awatori Mixer"). Next, 0.1 g of the resulting mixture was placed on an aluminum pan (manufactured by Hitachi High-Tech Science, "RDC Pan", "RDC Pan cover") and measured using a differential scanning calorimeter in a temperature range of 40 ° C. to 250 ° C. Differential scanning calorimetry is performed at a heating rate of 5°C/min. The reaction initiation temperature refers to the temperature at which the calorific value reaches 10% of the calorific value peak, and when there are multiple calorific value peaks, the reaction initiation temperature is the temperature at which the maximum calorific value peak reaches 10%. can be
Examples of the differential scanning calorimeter include DSC200 (manufactured by Hitachi High-Tech Science).

Specific examples of the thermosetting agent according to aspect 1 of the present invention include 4,4′-bis(aminophenoxy)benzophenone, 4,4′-diaminodiphenyl ketone, and compounds represented by the following formula (7). , 4,4′-diaminodiphenyl sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, bis(3-aminophenyl) sulfone and the like.

In the liquid crystal display element sealant of the first aspect of the present invention, the preferable lower limit of the content of the thermosetting agent according to the first aspect of the present invention to 100 parts by mass of the curable resin is 2.0 parts by mass, and the preferable upper limit is 14.8. part by mass. When the content of the thermosetting agent according to aspect 1 of the present invention is 2.0 parts by mass or more with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements is superior in curability and adhesiveness. Become. When the content of the thermosetting agent according to aspect 1 of the present invention is 14.8 parts by mass or less with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements has low liquid crystal contamination and storage stability. become excellent. A more preferable lower limit of the content of the thermosetting agent according to the first aspect of the present invention is 3.0 parts by mass, and a more preferable upper limit is 9.6 parts by mass with respect to 100 parts by mass of the curable resin.
Further, in the liquid crystal display element sealant of the first aspect of the present invention, when an epoxy compound described later as the curable resin is contained, the content of the thermosetting agent according to the first aspect of the present invention with respect to one equivalent of the epoxy compound A preferred lower limit is 0.5 equivalents, and a preferred upper limit is 2.0 equivalents. When the content of the thermosetting agent according to aspect 1 of the present invention is 0.5 equivalents or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the thermosetting agent according to the first aspect of the present invention is 2.0 equivalents or less per equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements is excellent in low liquid crystal contamination resistance and storage stability. becomes. A more preferable lower limit of the content of the thermosetting agent according to the first aspect of the present invention is 0.8 equivalents, and a more preferable upper limit thereof is 1.3 equivalents relative to 1 equivalent of the epoxy compound.

The sealant for a liquid crystal display element according to aspect 2 of the first aspect of the present invention has, as the thermosetting agent according to the first aspect of the present invention, two or more primary amino groups in one molecule, and the above formula (2-1), ( 2-2), (2-3), or a compound having a structure represented by (2-4) (hereinafter also referred to as "thermosetting agent according to aspect 1 of the present invention"). By containing the thermosetting agent according to aspect 2 of the present invention, the sealant for liquid crystal display elements of aspect 2 of the present invention has excellent storage stability, adhesiveness, and low liquid crystal contamination during panel production. become excellent.

The thermosetting agent according to aspect 1 of the present invention has a structure represented by formula (2-1), (2-2), (2-3), or (2-4). The structures represented by formulas (2-1), (2-2), (2-3), and (2-4) contain a sulfonyl group and an aromatic ring. By having the sulfonyl group, the thermosetting agent according to the first aspect of the present invention is less likely to be eluted into the liquid crystal. From the viewpoint of reactivity, it is most preferable that the thermosetting agent according to aspect 1 of the present invention has one sulfonyl group per molecule. Moreover, by having the aromatic ring, the thermosetting agent according to the first aspect of the present invention has excellent thermal latency, and the obtained sealing agent for liquid crystal display elements has excellent storage stability. The thermosetting agent according to the first aspect of the present invention preferably has two or more aromatic rings in one molecule. From the viewpoint of reactivity, it is preferable that the thermosetting agent according to the first aspect of the present invention has 4 or less aromatic rings per molecule.

Examples of the aromatic ring possessed by the thermosetting agent according to the first aspect of the present invention include a benzene ring, a naphthalene ring, an anthracene ring, and the like. Among them, a benzene ring is preferred.

The thermosetting agent according to aspect 1 of the present invention has two or more primary amino groups ( _-NH2 groups) in one molecule. By having two or more primary amino groups in one molecule, the thermosetting agent according to the first aspect of the present invention has excellent adhesiveness.
Moreover, from the viewpoint of storage stability, the thermosetting agent according to the first aspect of the present invention preferably has 4 or less primary amino groups per molecule.
The thermosetting agent according to aspect 1 of the present invention preferably has the primary amino groups at the ends of the main chain, and more preferably has the primary amino groups at both ends of the main chain.

The thermosetting agent according to aspect 2 of the first aspect of the present invention can make the obtained sealing agent for liquid crystal display elements more excellent in all of storage stability, adhesiveness, and low liquid crystal contamination during panel production. , preferably have a structure represented by the above formula (3-1), (3-2), or (3-3).

Specifically, the thermosetting agent according to the first aspect 2 of the present invention includes the above formulas (4-1), (4-2), (4-3), (4-4), (4-5), Alternatively, a compound represented by (4-6) is preferred. Among them, a compound represented by the following formula (4-1) is more preferable.

As the compound represented by the above formula (4-1), 4,4'-diaminodiphenylsulfone and bis(3-aminophenyl)sulfone are preferably used.

In the liquid crystal display element sealant of the first aspect of the present invention, the preferred lower limit of the content of the thermosetting agent according to the first aspect of the present invention 2 to 100 parts by mass of the curable resin is 2.0 parts by mass, and the preferred upper limit is 14.3. part by mass. When the content of the thermosetting agent according to aspect 2 of the present invention is 2.0 parts by mass or more relative to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements is superior in curability and adhesiveness. Become. When the content of the thermosetting agent according to aspect 2 of the present invention is 14.3 parts by mass or less with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements has low liquid crystal contamination and storage stability. become excellent. A more preferable lower limit of the content of the thermosetting agent according to the first aspect of the present invention 2 is 2.8 parts by mass, and a more preferable upper limit is 10.8 parts by mass with respect to 100 parts by mass of the curable resin.
Further, in the liquid crystal display element sealant of the first aspect 2 of the present invention, when an epoxy compound described later as the curable resin is contained, the content of the thermosetting agent according to the first aspect 2 of the present invention with respect to 1 equivalent of the epoxy compound A preferred lower limit is 0.5 equivalents, and a preferred upper limit is 2 equivalents. When the content of the thermosetting agent according to aspect 2 of the present invention is 0.5 equivalents or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements is excellent in curability and adhesiveness. When the content of the thermosetting agent according to aspect 2 of the present invention is 2 equivalents or less with respect to 1 equivalent of the epoxy compound, the resulting sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance. . A more preferable lower limit of the content of the thermosetting agent according to aspect 2 of the present invention is 0.8 equivalents, and a more preferable upper limit thereof is 1.5 equivalents relative to 1 equivalent of the epoxy compound.

The sealant for a liquid crystal display element of the third aspect of the first aspect of the present invention has two or more hydrazide groups represented by the above formula (5) in one molecule as the thermosetting agent according to the first aspect of the present invention, and has an aromatic ring and Includes polyvalent hydrazide compounds with attached sulfonyl groups. A polyvalent hydrazide compound having two or more hydrazide groups represented by the above formula (5) in one molecule and having a sulfonyl group bonded to an aromatic ring is also one aspect of the present invention.
By containing the polyhydrazide compound of the present invention, the sealant for a liquid crystal display element of the first embodiment of the present invention 3 is excellent in all of storage stability, adhesiveness, low liquid crystal contamination resistance, and heat resistance. .

The polyhydrazide compounds of the present invention have a sulfonyl group attached to an aromatic ring. By having the sulfonyl group, the polyvalent hydrazide compound of the present invention has a strong intermolecular interaction and high crystallinity, and thus has excellent heat resistance as compared with various hydrazide curing agents. From the viewpoint of adhesiveness, the number of sulfonyl groups in the polyhydrazide compound of the present invention is preferably 4 or less per molecule.
Moreover, by having the aromatic ring, the polyhydrazide compound of the present invention has excellent compatibility with a curable resin, and the obtained sealing agent for liquid crystal display elements has excellent adhesiveness. The polyhydrazide compound of the present invention preferably has two or more aromatic rings in one molecule. From the viewpoint of adhesiveness, it is preferable that the polyhydrazide compound of the present invention has 6 or less aromatic rings per molecule.

Examples of the aromatic ring of the polyhydrazide compound of the present invention include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring and the like. In addition, the aromatic ring may contain heteroatoms such as oxygen, nitrogen, sulfur and phosphorus. Among them, a benzene ring is preferred.

The polyvalent hydrazide compound of the present invention has two or more hydrazide groups represented by the above formula (5) in one molecule. By having two or more hydrazide groups represented by the above formula (5) in one molecule, the polyvalent hydrazide compound of the present invention has excellent reactivity.
Moreover, from the viewpoint of storage stability, the polyhydrazide compound of the present invention preferably has 8 or less hydrazide groups represented by the above formula (5) per molecule.
The polyvalent hydrazide compound of the present invention preferably has a hydrazide group represented by the above formula (5) at the end of the main chain, and has a hydrazide group represented by the above formula (5) at all ends of the main chain. It is more preferable to have

The polyhydrazide compound of the present invention can make the resulting sealing agent for liquid crystal display elements more excellent in all of storage stability, adhesiveness, and heat resistance. It is preferable to have a structure that

Specific examples of the polyvalent hydrazide compound of the present invention include compounds having 1 to 8 diphenylsulfone skeletons per molecule and 2 to 8 hydrazide groups per molecule. Among them, a compound represented by the following formula (8) is preferable.

In formula (8), each R is independently a bond, a saturated hydrocarbon chain, an unsaturated hydrocarbon chain, a heteroatom, or an aromatic ring. Also, an oxygen atom may be present between R and the benzene ring.

When R in the above formula (8) is an aromatic ring, examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and perylene ring. The aromatic ring may also contain heteroatoms such as oxygen, nitrogen, sulfur and phosphorus.

Among the compounds represented by the above formula (8), compounds represented by the following formula (9) and compounds represented by the following formula (10) are preferable.

From the viewpoint of adhesiveness, a compound represented by the following formula (11) is preferable as the polyhydrazide compound of the present invention.

Examples of the method for producing the polyhydrazide compound of the present invention include the following methods.
That is, first, a compound having a sulfonyl group, an aromatic ring and a carboxyl group is stirred in an alcohol solvent while refluxing with an acid catalyst to synthesize an esterified product. Then, the resulting esterified product is again stirred with hydrazine hydrate in an alcohol solvent at room temperature (1°C to 30°C) to produce the polyhydric hydrazide compound of the present invention.
Further, in a solvent, an epoxy compound having a sulfonyl group and an aromatic ring is stirred together with a compound having an ester bond and a phenolic hydroxyl group in the presence of triphenylphosine, and then mixed with hydrazine hydrate at room temperature (1° C. to It can also be produced by stirring under the condition of 30°C.
Furthermore, in a solvent, a compound having a sulfonyl group, an aromatic ring and a carboxyl group is stirred together with a compound having an amino group and an ester bond in the presence of a condensing agent, and then mixed with hydrazine hydrate at room temperature (1° C. to It can also be produced by stirring under the condition of 30°C.

In the liquid crystal display element sealant of the first aspect of the present invention, the preferred lower limit of the content of the polyhydrazide compound of the present invention is 3 parts by mass, and the preferred upper limit thereof is 70 parts by mass relative to 100 parts by mass of the curable resin. When the content of the polyhydrazide compound of the present invention with respect to 100 parts by mass of the curable resin is 3 parts by mass or more, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the polyhydrazide compound of the present invention is 70 parts by mass or less with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements has excellent heat resistance and storage stability. A more preferable lower limit of the content of the polyhydrazide compound of the present invention is 6 parts by mass, and a more preferable upper limit thereof is 35 parts by mass based on 100 parts by mass of the curable resin.
Further, in the liquid crystal display element sealant of Embodiment 1 of the present invention 3, when it contains an epoxy compound to be described later as the curable resin, the preferred lower limit of the content of the polyhydrazide compound of the present invention with respect to 1 equivalent of the epoxy compound is 0.5 equivalents, the preferred upper limit is 2.0 equivalents. When the content of the polyhydrazide compound of the present invention is 0.5 equivalents or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the polyhydrazide compound of the present invention is 2.0 equivalents or less relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent storage stability. A more preferable lower limit of the content of the polyhydrazide compound of the present invention to 1 equivalent of the epoxy compound is 0.8 equivalents, and a more preferable upper limit thereof is 1.2 equivalents.

In the sealing compound for a liquid crystal display element of the second aspect of the present invention, the thermosetting agent has a total of two or more primary amino groups or hydrazide groups in one molecule, and the constituent atoms have an average charge is 0.4a.d below the atomic intrinsic theoretical charge. u. Including compounds having atoms larger than or equal to (hereinafter also referred to as "thermosetting agent according to the second aspect of the present invention"). By containing the thermosetting agent according to Invention 2, the sealant for liquid crystal display elements of Invention 2 is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.

The thermosetting agent according to the second aspect of the present invention has at least two primary amino groups or hydrazide groups in total in one molecule. The thermosetting agent according to the second aspect of the present invention has at least two or more primary amino groups or hydrazide groups in one molecule. It will be excellent in quality.

In the thermosetting agent according to the second aspect of the present invention, the constituent atoms have an average charge of 0.4 a. u. or larger atoms. The thermosetting agent according to the present invention 2 has an average charge of 0.4 a. u. By having atoms as large as above, the sealant for a liquid crystal display element of the present invention 2 is excellent in storage stability and low liquid crystal contamination. The thermosetting agent according to the second aspect of the present invention preferably has an atom whose average charge is 0.6 or more larger than the theoretical charge inherent to the atom, more preferably 0.65 or more, among the constituent atoms. preferable.

The thermosetting agent according to the present invention 2 has line symmetry or point symmetry, and the average charge is 0.4 a. u. Preferably, the larger atom is the center atom of symmetry (or the atom closest to the center if there is no atom at the center). The thermosetting agent according to the present invention 2 has line symmetry or point symmetry, and the average charge is 0.4 a. u. Since the larger atom is the atom at the center of symmetry (the atom closest to the center if there is no atom at the center), the sealant for a liquid crystal display element of the present invention 2 has storage stability and low liquid crystal contamination. become excellent.

The preferred lower limit of the reaction initiation temperature of the thermosetting agent according to the second aspect of the invention with bisphenol F diglycidyl ether is 120°C. When the reaction initiation temperature is 120° C. or higher, the obtained sealing agent for liquid crystal display elements has excellent storage stability. A more preferable lower limit of the reaction initiation temperature is 130°C, and a further preferable lower limit is 135°C.
From the viewpoint of curability of the obtained sealing agent for liquid crystal display elements, the upper limit of the reaction initiation temperature is preferably 220°C, more preferably 215°C, and still more preferably 210°C.

The thermosetting agent according to the present invention 2 preferably has at least one structure represented by the above formula (1-1) or the above formula (1-2). Since the thermosetting agent according to the second aspect of the present invention has a structure represented by at least one of the above formulas (1-1) and (1-2), the sealing agent for liquid crystal display elements of the second aspect of the present invention has storage stability. and low liquid crystal contamination.

Specific examples of the thermosetting agent according to the second aspect of the present invention include, for example, 4,4'-bis(aminophenoxy)benzophenone (atoms (central carbon atoms), reaction initiation temperature with bisphenol F diglycidyl ether 135 ° C.), 4,4'-diaminodiphenyl ketone (atoms whose average charge is 0.41 au or more than the theoretical charge inherent to the atom (center carbon atom), reaction initiation temperature with bisphenol F diglycidyl ether 180 ° C.), the compound represented by the above formula (7) (average charge is 0.68 a.u. than the theoretical charge inherent to the atom) (210° C. at reaction initiation temperature with bisphenol F diglycidyl ether) and the like.

In the liquid crystal display element sealant of Invention 2, the preferable lower limit of the content of the thermosetting agent according to Invention 2 to 100 parts by mass of the curable resin is 2.0 parts by mass, and the preferable upper limit is 14.8 parts by mass. . When the content of the thermosetting agent according to the present invention 2 is 2.0 parts by mass or more with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. Since the content of the thermosetting agent according to the present invention 2 is 14.8 parts by mass or less with respect to 100 parts by mass of the curable resin, the obtained sealing agent for liquid crystal display elements is excellent in low liquid crystal contamination resistance and storage stability. becomes. A more preferable lower limit of the content of the thermosetting agent according to the present invention 2 to 100 parts by mass of the curable resin is 3.0 parts by mass, and a more preferable upper limit is 9.6 parts by mass.
In addition, when the sealing compound for a liquid crystal display element of Invention 2 contains an epoxy compound to be described later as the curable resin, the preferred lower limit of the content of the thermosetting agent according to Invention 2 with respect to 1 equivalent of the epoxy compound is 0. .5 equivalents, with a preferred upper limit of 2.0 equivalents. When the content of the thermosetting agent according to the present invention 2 is 0.5 equivalents or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. By setting the content of the thermosetting agent according to the present invention 2 to 1 equivalent of the epoxy compound to be 2.0 equivalents or less, the obtained sealing agent for liquid crystal display elements is excellent in low liquid crystal contamination resistance and storage stability. . A more preferable lower limit of the content of the heat curing agent according to the present invention 2 to 1 equivalent of the epoxy compound is 0.8 equivalents, and a more preferable upper limit thereof is 1.3 equivalents.

The sealant for liquid crystal display elements of the present invention contains a curable resin.
Examples of the curable resin include epoxy compounds, (meth)acrylic compounds, polyurethane compounds, and phenol compounds. Especially, it is preferable that the said curable resin contains an epoxy compound.
In addition, in this specification, the above-mentioned "(meth)acryl" means acryl or methacryl.

Examples of the epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, bisphenol S type epoxy compounds, 2,2′-diallylbisphenol A type epoxy compounds, and hydrogenated bisphenol type epoxy compounds. , propylene oxide-added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, ortho-cresol Novolak-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolac-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like. be done.

Commercially available bisphenol A type epoxy compounds include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
Commercially available bisphenol F-type epoxy compounds include, for example, jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation) and EPICLON EXA-830CRP (manufactured by DIC Corporation).
Examples of commercially available bisphenol E type epoxy compounds include Epomic R710 (manufactured by Mitsui Chemicals, Inc.).
Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA-1514 (manufactured by DIC Corporation).
Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available hydrogenated bisphenol epoxy compounds include, for example, EPICLON EXA-7015 (manufactured by DIC).
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
Commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenolic novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC).
Commercially available dicyclopentadiene novolac type epoxy compounds include, for example, EPICLON HP-7200 (manufactured by DIC Corporation).
Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalenephenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation) and the like.
Commercially available rubber-modified epoxy compounds include, for example, YR-450 and YR-207 (both manufactured by Nippon Steel Chemical & Materials) and Epolead PB (manufactured by Daicel).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei), jER1031, and jER1032. (all manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.

Partially (meth)acryl-modified epoxy compounds are also suitably used as the epoxy compound.
In the present specification, the partially (meth)acrylic-modified epoxy compound is obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups with (meth)acrylic acid. It means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in the molecule.
In addition, in this specification, the said "(meth)acryloyl" means acryloyl or methacryloyl.

Examples of commercially available partially (meth)acrylic-modified epoxy compounds include UVACURE1561, KRM8030, and KRM8287 (all manufactured by Daicel Allnex).

Moreover, the curable resin preferably contains the (meth)acrylic compound.
Examples of the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among them, epoxy (meth)acrylate is preferred. From the viewpoint of reactivity, the (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule.
In this specification, the "(meth)acrylic compound" means a compound having a (meth)acryloyl group, excluding the partially (meth)acryl-modified epoxy compound. Further, the above "(meth)acrylate" means acrylate or methacrylate, and the above "epoxy(meth)acrylate" is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid. represents

Among the above (meth)acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl ( meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-Phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbi tall (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imido (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-( meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate and the like.

Among the above (meth)acrylic acid ester compounds, bifunctional ones include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate , dimethyloldicyclopentadienyl di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate and the like.

Further, among the above (meth)acrylic acid ester compounds, trifunctional or higher ones include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri( meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

As the epoxy compound serving as a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compound as the curable resin contained in the sealing agent for liquid crystal display elements of the present invention can be used.

Commercially available epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Allnex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
Examples of epoxy (meth)acrylates manufactured by Daicel Allnex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECR YL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, KRM8076 and the like.
Examples of epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
Examples of the epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include, for example, Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA and the like.
Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

The urethane (meth)acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.

Examples of isocyanate compounds that are raw materials for the urethane (meth)acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4 '-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, and the like.

In addition, as the isocyanate compound that is a raw material for the urethane (meth)acrylate, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, dihydric alcohol mono(meth)acrylates, trihydric alcohol mono(meth)acrylates and di(meth)acrylates. , epoxy (meth)acrylate, and the like.
Examples of the hydroxyalkyl mono(meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. mentioned.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerin and the like.
As said epoxy (meth)acrylate, a bisphenol A type epoxy (meth)acrylate etc. are mentioned, for example.

Examples of commercially available urethane (meth) acrylates include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. acrylate, urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth)acrylates manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth)acrylates manufactured by Daicel Allnex include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, and EBECRYL5. 129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc. mentioned.
Examples of the urethane (meth)acrylate manufactured by Neagari Kogyo Co., Ltd. include, for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN- 7100, Artresin UN-9000A, Artresin UN-9000H and the like.
The urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include, for example, U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA- 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A and the like.
Examples of the urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. be done.

When the curable resin contains the (meth)acrylic compound in addition to the epoxy compound, or when the partially (meth)acryl-modified epoxy compound is contained, the epoxy group in the curable resin and the (meth) It is preferable that the ratio of (meth)acryloyl groups in the total amount of acryloyl groups is 30 mol % or more and 95 mol % or less. When the ratio of the (meth)acryloyl group is within this range, the resulting sealing compound for liquid crystal display elements is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.

From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, or —NH ₂ group.

The sealant for liquid crystal display elements of the present invention preferably contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino) -2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2 ,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)- 2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2-(acetoxyimino)-1 -(4-(4-(2-hydroxyethoxy)phenylthio)phenyl)propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.
The photopolymerization initiators may be used alone, or two or more of them may be used in combination.

The preferable lower limit of the content of the photopolymerization initiator is 0.5 parts by mass, and the preferable upper limit thereof is 10 parts by mass with respect to 100 parts by mass of the curable resin. When the content of the photopolymerization initiator is within this range, the resulting sealing compound for liquid crystal display elements is excellent in storage stability and photocurability while suppressing the occurrence of liquid crystal contamination. A more preferable lower limit for the content of the photopolymerization initiator is 1 part by mass, and a more preferable upper limit is 7 parts by mass.

The sealing compound for liquid crystal display elements of the present invention preferably contains a thermal radical polymerization initiator.
Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, an initiator composed of an azo compound (hereinafter also referred to as "azo initiator") is preferable from the viewpoint of suppressing liquid crystal contamination.
The thermal radical polymerization initiators may be used alone, or two or more of them may be used in combination.

Examples of the azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, one having a polyethylene oxide structure is preferable.
Specific examples of the azo compound include polycondensates of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol, 4,4′-azobis(4-cyanopentanoic acid) and terminal Examples include polycondensates of polydimethylsiloxane having amino groups.
Examples of the azo initiator include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, V-65, V-501 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). be done.

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides and peroxydicarbonates.

The content of the thermal radical polymerization initiator has a preferable lower limit of 0.1 parts by mass and a preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the curable resin. When the content of the thermal radical polymerization initiator is within this range, the resulting sealing compound for liquid crystal display elements is excellent in storage stability and thermosetting property while suppressing the occurrence of liquid crystal contamination. A more preferable lower limit to the content of the thermal radical polymerization initiator is 0.3 parts by mass, and a more preferable upper limit is 5 parts by mass.

The sealant for liquid crystal display elements of the present invention preferably contains a curing accelerator. By containing the curing accelerator, the curing time can be shortened to improve the productivity, and the obtained sealing compound for liquid crystal display elements has excellent adhesiveness to the substrate and the alignment film.

As the curing accelerator, an imidazole-based curing accelerator is preferably used from the viewpoint of reaction speed and adhesiveness.
Examples of the imidazole curing accelerator include 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, 2-phenyl -4-methyl-5-hydroxymethylimidazole and the like.

The content of the curing accelerator has a preferable lower limit of 0.05 parts by mass and a preferable upper limit of 3 parts by mass with respect to 100 parts by mass of the curable resin. When the content of the curing accelerator is within this range, the obtained sealing compound for liquid crystal display elements is excellent in reaction speed and adhesiveness. A more preferable lower limit for the content of the curing accelerator is 0.1 part by mass.

The sealant for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving coefficient of linear expansion, improving moisture resistance of the cured product, and the like.

An inorganic filler or an organic filler can be used as the filler.
Examples of inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.
The above fillers may be used alone, or two or more of them may be used in combination.

A preferable lower limit of the content of the filler in 100 parts by mass of the sealing compound for liquid crystal display elements of the present invention is 10 parts by mass, and a preferable upper limit thereof is 70 parts by mass. When the content of the filler is within this range, the effect of improving adhesiveness, etc., is excellent without deteriorating coating properties, etc. A more preferable lower limit of the filler content is 20 parts by mass, and a more preferable upper limit is 60 parts by mass.

The sealing compound for liquid crystal display elements of the present invention may contain a silane coupling agent. The silane coupling agent mainly functions as an adhesion assistant for good adhesion between the liquid crystal display element sealing compound and the substrate.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. Among them, 3-glycidoxypropyltrimethoxysilane is preferred.
The silane coupling agents may be used alone, or two or more of them may be used in combination.

A preferable lower limit of the content of the silane coupling agent in 100 parts by mass of the liquid crystal display element sealing compound of the present invention is 0.1 parts by mass, and a preferable upper limit thereof is 10 parts by mass. When the content of the silane coupling agent is within this range, the obtained sealing compound for liquid crystal display elements is excellent in the effect of improving adhesiveness while suppressing the occurrence of liquid crystal contamination. A more preferable lower limit to the content of the silane coupling agent is 0.3 parts by mass, and a more preferable upper limit is 5 parts by mass.

The sealant for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the light shielding agent, the sealant for liquid crystal display elements of the present invention can be suitably used as a light shielding sealant.

Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.

Titanium black is a substance that exhibits a higher transmittance for light in the vicinity of the ultraviolet region, particularly light with a wavelength of 370 nm or more and 450 nm or less, than average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting a light-shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light of wavelengths in the visible light region, while transmitting light of wavelengths in the vicinity of the ultraviolet region. It is a light-shielding agent with Therefore, by using a photopolymerization initiator capable of initiating a reaction by light having a wavelength at which the transmittance of the titanium black increases, the photocuring property of the sealant for a liquid crystal display element of the present invention is further increased. be able to. On the other hand, as the light shielding agent contained in the sealant for liquid crystal display elements of the present invention, a highly insulating substance is preferable, and titanium black is also suitable as the highly insulating light shielding agent.
The above titanium black preferably has an optical density (OD value) per 1 μm of 3 or more, more preferably 4 or more. The higher the light shielding property of the titanium black, the better. Although there is no particular upper limit for the OD value of the titanium black, it is usually 5 or less.

The above titanium black exerts a sufficient effect even if it is not surface-treated, but it can also be used when the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide. Surface-treated titanium blacks, such as those coated with inorganic components such as zirconium and magnesium oxide, can also be used. Among them, those treated with an organic component are preferable because they can further improve the insulating properties.
Further, the liquid crystal display device manufactured using the sealing agent for a liquid crystal display device of the present invention in which the above-described titanium black is blended as a light shielding agent has sufficient light shielding properties, so that light does not leak out and has high contrast. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Kasei Co., Ltd., and the like.
Examples of titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.

The specific surface area of the titanium black has a preferred lower limit of 13 m ² /g, a preferred upper limit of 30 m ² /g, a more preferred lower limit of 15 m ² /g, and a more preferred upper limit of 25 m ² /g.
The preferred lower limit of the volume resistivity of titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The primary particle size of the light shielding agent is not particularly limited as long as it is equal to or smaller than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. When the primary particle size of the light shielding agent is within this range, the obtained sealing agent for liquid crystal display elements can be made more excellent in light shielding properties without deteriorating the applicability or the like. The primary particle size of the light shielding agent has a more preferable lower limit of 5 nm, a more preferable upper limit of 200 nm, a still more preferable lower limit of 10 nm, and a still more preferable upper limit of 100 nm.
The primary particle size of the light shielding agent can be measured by dispersing the light shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

A preferable lower limit of the content of the light shielding agent in 100 parts by mass of the liquid crystal display element sealing compound of the present invention is 5 parts by mass, and a preferable upper limit thereof is 80 parts by mass. When the content of the light-shielding agent is within this range, the obtained sealant for liquid crystal display elements exhibits excellent light-shielding properties without significantly deteriorating the adhesiveness, strength after curing, and drawability. be able to. A more preferable lower limit of the content of the light shielding agent is 10 parts by mass, a more preferable upper limit is 70 parts by mass, a still more preferable lower limit is 30 parts by mass, and a further preferable upper limit is 60 parts by mass.

The sealant for liquid crystal display elements of the present invention may further contain, if necessary, stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, and the like. It may contain an agent.

As a method for producing the liquid crystal display element sealing compound of the present invention, for example, a mixer is used to mix a curable resin, a thermosetting agent, and a photoradical polymerization initiator to be added as necessary. and the like.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

The preferable lower limit of the 10% weight loss temperature after curing of the sealant for liquid crystal display elements of the present invention is 350°C. Since the 10% weight loss temperature after curing is 350° C. or higher, the sealant for liquid crystal display elements of the present invention can be suitably used as an adhesive or the like that particularly requires heat resistance. Although there is no particular upper limit for the 10% weight loss temperature after curing, the practical upper limit is 450°C.
The 10% weight loss temperature is derived by performing thermogravimetric measurement at a temperature elevation rate of 10°C/min from 30°C to 450°C using a simultaneous differential thermogravimetric measurement device. can be done. Examples of the simultaneous differential thermal thermogravimetric measurement device include STA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.). Further, as the cured product for measuring the 10% weight loss temperature, the liquid crystal display element sealant is irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and then cured by heating at 120 ° C. for 60 minutes. A material having a thickness of 500 μm is used.

By blending the conductive fine particles into the liquid crystal display element sealant of the present invention, a vertically conducting material can be produced.
As the conductive fine particles, for example, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, and the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

A liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention is also one aspect of the present invention.

As the liquid crystal display element of the present invention, a liquid crystal display element having a narrow frame design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display section is 2 mm or less.
Moreover, it is preferable that the coating width of the sealant for a liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.

The sealing compound for liquid crystal display elements of the present invention can be suitably used for manufacturing liquid crystal display elements by the liquid crystal dropping method.
Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of forming a frame-shaped seal pattern by applying the sealant for a liquid crystal display element of the present invention to a substrate by screen printing, dispenser coating, or the like is performed. Next, a step of applying liquid crystal microdroplets to the entire surface of the frame of the seal pattern while the sealant for a liquid crystal display element of the present invention is in an uncured state, and immediately superimposing another substrate is performed. After that, a liquid crystal display element can be obtained by a method of performing a step of heating and curing the sealant. Moreover, before the step of heating and curing the sealant, a step of temporarily curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low-liquid-crystal contamination property can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealing agent for liquid crystal display elements, and a polyhydric hydrazide compound that can be used for the sealing agent for liquid crystal display elements.

FIG. 1 is a polarizing microscope image of a liquid crystal display element produced using the liquid crystal display element sealing compound obtained in Example 7 in the evaluation of "(low liquid crystal contamination)". FIG. 2 is a polarizing microscope image of a liquid crystal display device produced using the liquid crystal display device sealant obtained in Comparative Example 5 in the evaluation of “(low liquid crystal contamination)”.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Preparation of compound represented by formula (7))
A methyl ester was synthesized by stirring 200 g of 4,4-diphenyldicarboxysulfonic acid with 0.5 equivalent of sulfuric acid in 2 L of methanol solvent under reflux for 3 days. Then, the obtained solution containing the methyl ester was cooled to room temperature and then neutralized with an aqueous calcium hydrogencarbonate solution. After the solvent was distilled off from the neutralized solution under reduced pressure, the intermediate was purified by liquid separation with THF and brine. The resulting intermediate was again stirred in methanol solvent together with hydrazine hydrate under room temperature conditions to prepare the compound represented by the above formula (7).
The structure of the obtained compound represented by formula (7) was confirmed by ¹ H-NMR and FT-IR analysis.

(Examples 1 to 24, Comparative Examples 1 to 13)
According to the compounding ratios shown in Tables 1 to 3, each material was mixed using a planetary stirrer (manufactured by Thinky Co., Ltd., "Awatori Mixer"), and then further mixed using three rolls. Sealants for liquid crystal display elements of Examples 1 to 24 and Comparative Examples 1 to 13 were prepared.
For all atoms constituting each thermosetting agent used in Examples 1 to 6 and Comparative Examples 1 to 4, the value obtained by subtracting the value of the theoretical charge inherent to the atom from the value of the average charge was calculated. Table 1 shows the maximum value among the values obtained for each atom.
In addition, the reaction initiation temperature with bisphenol F diglycidyl ether in each thermosetting agent used in Examples 1 to 6 and Comparative Examples 1 to 4 was measured by the following method. That is, first, 10 g of the thermosetting agent and 100 g of bisphenol F diglycidyl ether were stirred at a stirring speed of 2000 rpm for 1 minute using a planetary stirrer (manufactured by THINKY Co., Ltd., "Awatori Mixer"). Next, 0.1 g of the resulting mixture was placed on an aluminum pan (manufactured by Hitachi High-Tech Science, "RDC Pan", "RDC Pan cover"), and a differential scanning calorimeter (manufactured by Hitachi High-Tech Science, "DSC200") was used. Differential scanning calorimetry was performed at a temperature range of 40° C. to 250° C. and a heating rate of 5° C./min. The temperature at which the calorific value reached 10% of the calorific value peak (when there were multiple calorific value peaks, the temperature at which the calorific value reached 10% of the maximum calorific value peak) was defined as the reaction initiation temperature. Table 1 shows the results.

<Evaluation>
The sealants for liquid crystal display elements obtained in Examples 1 to 24 and Comparative Examples 1 to 13 were evaluated as follows. The results are shown in Tables 1-3.

(Storage stability)
The initial viscosities immediately after production and the viscosities after storage at 25° C. for 1 week after production were measured for each sealing compound for liquid crystal display elements obtained in Examples 1 to 24 and Comparative Examples 1 to 13. (Viscosity after storage) / (initial viscosity) is defined as the viscosity increase rate, and "○" indicates that the viscosity increase rate is less than 2.0, and "△" indicates that the viscosity increase rate is 2.0 or more and less than 3.0. , 3.0 or more, the storage stability was evaluated as "x".
The viscosity of the liquid crystal display element sealant was measured using an E-type viscometer (“DV-III” manufactured by BROOK FIELD) at 25° C. and a rotational speed of 1.0 rpm.

(Adhesiveness)
1 part by mass of spacer fine particles was dispersed in 100 parts by mass of each sealing agent for liquid crystal display elements obtained in Examples 1 to 24 and Comparative Examples 1 to 13. Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used as the spacer fine particles. Next, a liquid crystal display element sealant in which spacer particles were dispersed was minutely dropped onto one of the two glass substrates (length 4.5 mm, width 2.5 mm) with an ITO thin film. Another ITO thin film-coated glass substrate was attached to this in a cross shape, irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and then heated at 120° C. for 60 minutes to obtain an adhesive test piece. When the edge of the substrate in the prepared adhesive test piece was pushed at a speed of 5 mm/min using a metal cylinder with a radius of 5 mm, the strength at which panel peeling occurred was measured.
If the value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) is 3.0 kgf/cm or more, "○", more than 2.0 kgf/cm and less than 3.0 kgf/cm Adhesiveness was evaluated as "Δ" when it was not more than 2.0 kgf/cm, and as "X" when it was 2.0 kgf/cm or less.
Further, a glass substrate with a polyimide alignment film for TN (manufactured by Nissan Chemical Industries, Ltd., "SE6414") was used instead of the glass substrate with the ITO thin film, and the adhesion was evaluated in the same manner.

(low liquid crystal contamination)
1 mass of spacer fine particles having an average particle diameter of 7 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) was added to 100 parts by mass of each sealing agent for liquid crystal display elements obtained in Examples 1 to 24 and Comparative Examples 1 to 13. The parts were dispersed, filled in a syringe, and defoamed with a centrifugal deaerator (manufactured by Musashi Engineering Co., Ltd., "Awatron AW-1"). Using a dispenser, the sealant for liquid crystal display elements after defoaming treatment is applied to two alignment films and under the conditions of a nozzle diameter of 0.4 mmφ, a nozzle gap of 42 μm, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. It was coated in a frame shape on one side of the glass substrate with the ITO thin film. RB-005 manufactured by Nissan Chemical Industries, Ltd. was used as the alignment film, and alignment treatment was performed by irradiating 300 mJ/cm ² of polarized light with a wavelength of 254 nm. At this time, the discharge pressure was adjusted so that the line width of the liquid crystal display element sealant was about 1.0 mm. Subsequently, microdroplets of liquid crystal ("JC-7129XX" manufactured by JNC TAIWAN Co., Ltd.) were applied dropwise to the entire surface of the frame of the liquid crystal display element sealing agent on the substrate coated with the liquid crystal display element sealing agent, and then again under vacuum. One substrate was pasted together. With respect to the bonded substrates, the portion of the liquid crystal display element sealing agent was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp to temporarily cure the liquid crystal display element sealing agent. Next, the composition was heated at 120° C. for 1 hour for final curing, thereby producing a liquid crystal display device.
The resulting liquid crystal display device was checked for alignment disorder (display unevenness) using a polarizing microscope ("VHX-5000" manufactured by Keyence Corporation). Orientation disorder was judged from color unevenness in the display portion, and the low liquid crystal contamination resistance was evaluated as "O" when no display unevenness was observed in the liquid crystal display element, and as "X" when display unevenness was observed. FIG. 1 shows a polarizing microscope image of a liquid crystal display element produced using the liquid crystal display element sealing compound obtained in Example 7, and produced using the liquid crystal display element sealing compound obtained in Comparative Example 5. FIG. 2 shows a polarizing microscope image of the liquid crystal display device.

(Preparation of compound represented by formula (9))
A methyl ester was synthesized by stirring 200 g of 4,4-diphenyldicarboxysulfonic acid with 0.5 equivalent of sulfuric acid in 2 L of methanol solvent under reflux for 3 days. Then, the obtained solution containing the methyl ester was cooled to room temperature and then neutralized with an aqueous calcium hydrogencarbonate solution. After the solvent was distilled off from the neutralized solution under reduced pressure, the intermediate was purified by liquid separation with THF and brine. The resulting intermediate was again stirred in methanol solvent together with hydrazine hydrate under room temperature conditions to prepare the compound represented by the above formula (9).
The structure of the obtained compound represented by formula (9) was confirmed by ¹ H-NMR and FT-IR analysis.

(Preparation of compound represented by formula (10))
By stirring 200 g of 2,4-dihydrodiphenylsulfone with 2.5 equivalents of ethyl chloroacetate and 2.5 equivalents of potassium carbonate in 2 L of N,N-dimethylformamide (DMF) solvent at 80° C. overnight, An ethyl ester was synthesized. Next, DMF was removed by distilling off the obtained solution containing the ethyl-esterified product under reduced pressure. Thereafter, 2 L of pure water was added and stirred to dissolve potassium carbonate, followed by filtration to purify the ethyl esterified product. The resulting ethyl-esterified product was stirred in 2 L of methanol solvent together with hydrazine hydrate under room temperature conditions to prepare the compound represented by the above formula (10).
The structure of the obtained compound represented by formula (10) was confirmed by ¹ H-NMR and FT-IR analysis.

(Preparation of compound represented by formula (11))
In 2 L of DMF solvent, 200 g of bis(3-amino-4-hydroxyphenyl)sulfone was stirred with 2.5 equivalents of ethyl chloroacetate and 2.5 equivalents of potassium carbonate at 80° C. overnight to give the ethyl ester. was synthesized. Next, DMF was removed by distilling off the obtained solution containing the ethyl-esterified product under reduced pressure. Thereafter, 2 L of pure water was added and stirred to dissolve potassium carbonate, followed by filtration to purify the ethyl esterified product. The resulting ethyl-esterified compound was stirred in 2 L of methanol solvent together with hydrazine hydrate under room temperature conditions to prepare the compound represented by the above formula (11).
The structure of the obtained compound represented by formula (11) was confirmed by ¹ H-NMR and FT-IR analysis.

(Examples 25-30, Comparative Examples 14 and 15)
According to the compounding ratio shown in Table 4, each material was mixed using a planetary stirrer (manufactured by THINKY Co., Ltd., "Awatori Mixer"), and then further mixed using three rolls. 25 to 30 and Comparative Examples 14 and 15 were prepared as sealants for liquid crystal display elements.

<Evaluation>
The sealants for liquid crystal display elements obtained in Examples 25 to 30 and Comparative Examples 14 and 15 were evaluated as follows. Table 4 shows the results.

(Storage stability)
The initial viscosities immediately after production and the viscosities after storage at 25° C. for 1 week after production were measured for each sealing agent for liquid crystal display elements obtained in Examples 25 to 30 and Comparative Examples 14 and 15. (Viscosity after storage) / (initial viscosity) is defined as the viscosity increase rate, and "○" indicates that the viscosity increase rate is less than 2.5, and "△" indicates that the viscosity increase rate is 2.5 or more and less than 4.0. , 4.0 or more, the storage stability was evaluated as "x".
The viscosity of the liquid crystal display element sealant was measured using an E-type viscometer (“DV-III” manufactured by BROOK FIELD) at 25° C. and a rotational speed of 1.0 rpm.

(Adhesiveness)
In 100 parts by mass of each sealing agent for liquid crystal display elements obtained in Examples 25 to 30 and Comparative Examples 14 and 15, 1 part by mass of spacer fine particles was dispersed. Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used as the spacer fine particles. Next, a liquid crystal display element sealant in which spacer particles were dispersed was minutely dropped onto one of the two glass substrates (length 4.5 mm, width 2.5 mm) with an ITO thin film. Another ITO thin film-coated glass substrate was attached to this in a cross shape, irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and then heated at 120° C. for 60 minutes to obtain an adhesive test piece. When the edge of the substrate in the prepared adhesive test piece was pushed at a speed of 5 mm/min using a metal cylinder with a radius of 5 mm, the strength at which panel peeling occurred was measured.
If the value obtained by dividing the obtained measured value (kgf) by the diameter (cm) of the joint is 2.0 kgf/cm or more, "◎", 1.5 kgf/cm or more and less than 2.0 kgf/cm Adhesiveness was evaluated as "○" when there was some, and as "X" when less than 1.5 kgf/cm.

(Heat-resistant)
The liquid crystal display element sealing agents obtained in Examples 25 to 30 and Comparative Examples 14 and 15 were irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and then heated at 120° C. for 60 minutes to obtain a thickness. A cured product of 500 μm was obtained. 10% weight when the obtained cured product is heated under conditions of 30 ° C. to 450 ° C. and 10 ° C./min using a differential thermal thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., "STA7200") Decay temperature was measured.
The heat resistance was evaluated as "○" when the 10% weight loss temperature was 350 ° C. or higher, "Δ" when it was 340 ° C. or higher and lower than 350 ° C., and "x" when it was lower than 340 ° C. .

(Examples 31-33, Comparative Examples 16 and 17)
According to the compounding ratio shown in Table 5, each material was mixed using a planetary stirrer (manufactured by THINKY Co., Ltd., "Awatori Mixer"), and then further mixed using a three-roll roll. Sealants for liquid crystal display elements of 31 to 33 and Comparative Examples 16 and 17 were prepared.

<Evaluation>
The sealants for liquid crystal display elements obtained in Examples 31 to 33 and Comparative Examples 16 and 17 were evaluated as follows. Table 5 shows the results.

(low liquid crystal contamination)
1 mass of spacer fine particles having an average particle diameter of 7 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) was added to 100 parts by mass of each sealing agent for liquid crystal display elements obtained in Examples 31 to 33 and Comparative Examples 16 and 17. The parts were dispersed, filled in a syringe, and defoamed with a centrifugal deaerator (manufactured by Musashi Engineering Co., Ltd., "Awatron AW-1"). Using a dispenser, the sealant for liquid crystal display elements after defoaming treatment is applied to two alignment films and under the conditions of a nozzle diameter of 0.4 mmφ, a nozzle gap of 42 μm, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. It was coated in a frame shape on one side of the glass substrate with the ITO thin film. RB-005 manufactured by Nissan Chemical Industries, Ltd. was used as the alignment film, and alignment treatment was performed by irradiating 300 mJ/cm ² of polarized light with a wavelength of 254 nm. At this time, the discharge pressure was adjusted so that the line width of the liquid crystal display element sealant was about 1.0 mm. Subsequently, microdroplets of liquid crystal ("4-pentyl-4-biphenylcarbonitrile" manufactured by Tokyo Kasei Kogyo Co., Ltd.) were applied to the entire frame of the liquid crystal display element sealing agent of the substrate coated with the liquid crystal display element sealing agent. It was applied dropwise and allowed to stand for 2 hours, and then the other substrate was bonded together under vacuum. The bonded substrates were allowed to stand still for 15 minutes after bonding, and then the liquid crystal display element sealant portion was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp to temporarily remove the liquid crystal display element sealant. Hardened. Next, the composition was heated at 120° C. for 1 hour for final curing, thereby producing a liquid crystal display device.
The resulting liquid crystal display device was checked for alignment disorder (display unevenness) using a polarizing microscope ("VHX-5000" manufactured by Keyence Corporation). Orientation disorder was judged from color unevenness in the display portion, and the low liquid crystal contamination resistance was evaluated as "O" when no display unevenness was observed in the liquid crystal display element, and as "X" when display unevenness was observed.

Claims

A sealant for a liquid crystal display element containing a curable resin and a thermosetting agent,
The thermosetting agent has a total of two or more primary amino groups and/or hydrazide groups in one molecule, and at least one of a sulfonyl group bonded to an aromatic ring and a carbonyl group bonded to an aromatic ring. A sealing compound for a liquid crystal display element, comprising a compound having
The thermosetting agent has a total of two or more primary amino groups and hydrazide groups in one molecule, and at least one of the following formula (1-1) and the following formula (1-2) 2. The sealant for a liquid crystal display element according to claim 1, comprising a compound having a structure of

In formulas (1-1) and (1-2), * represents a bonding position.
The thermosetting agent contains a compound having two or more primary amino groups in one molecule and having at least one structure of the formula (1-1) and the formula (1-2). Item 2. The sealant for liquid crystal display elements according to item 2.
3. The thermosetting agent according to claim 2, wherein the thermosetting agent includes a compound having a total of two or more primary amino groups and/or hydrazide groups in one molecule and having the structure of the formula (1-2). Sealant for liquid crystal display elements.
5. The sealant for a liquid crystal display element according to claim 4, wherein the thermosetting agent contains a compound having two or more hydrazide groups in one molecule and having the structure of formula (1-2).
The thermosetting agent has two or more primary amino groups in one molecule, and has the following formula (2-1), (2-2), (2-3), or (2-4) The sealant for a liquid crystal display element according to claim 1, comprising a compound having a structure represented by:

In formulas (2-1) to (2-4), * represents a bonding position.
A structure having two or more of the primary amino groups in one molecule and represented by the above formula (2-1), (2-2), (2-3), or (2-4) The sealing compound for a liquid crystal display element according to claim 6, wherein the compound has a structure represented by the following formula (3-1), (3-2), or (3-3).

In formulas (3-1) to (3-3), * represents a bonding position.
A structure having two or more of the primary amino groups in one molecule and represented by the above formula (2-1), (2-2), (2-3), or (2-4) is a compound represented by the following formula (4-1), (4-2), (4-3), (4-4), (4-5), or (4-6) The sealant for liquid crystal display elements according to claim 7.
2. The liquid crystal according to claim 1, wherein the thermosetting agent contains a polyvalent hydrazide compound having two or more hydrazide groups represented by the following formula (5) in one molecule and having a sulfonyl group bonded to an aromatic ring. Sealant for display elements.

In formula (5), * represents a binding position.
10. The sealing compound for liquid crystal display elements according to claim 9, wherein the polyhydrazide compound has a structure represented by the following formula (6).

In formula (6), R 1 to R 4 are each independently a group containing at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a nitrogen atom, a hydrogen atom, or , represents a linking group, and at least one of R 1 to R 4 is bonded to the hydrazide group represented by the formula (5).
11. The sealant for liquid crystal display elements according to claim 10, wherein at least one of R 1 to R 4 in the structure represented by formula (6) contains an amino group or a hydroxyl group.
A sealant for a liquid crystal display element containing a curable resin and a thermosetting agent,
The thermosetting agent has a total of two or more primary amino groups and/or hydrazide groups in one molecule, and the average charge among constituent atoms is 0.4 a. u. A sealant for a liquid crystal display element, comprising a compound having an atom larger than the above.
13. The sealing compound for a liquid crystal display element according to claim 12, wherein the thermosetting agent has a reaction initiation temperature with bisphenol F diglycidyl ether of 120[deg.] C. or higher.
14. The sealing compound for a liquid crystal display element according to claim 1, wherein said curable resin contains an epoxy compound.
15. The sealant for a liquid crystal display element according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the curable resin contains a (meth)acrylic compound. .
16. The sealant for liquid crystal display elements according to claim 1, which further contains a photopolymerization initiator.
17. The seal for liquid crystal display elements according to claim 1, further comprising a thermal radical polymerization initiator, agent.
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, wherein the 10% weight loss temperature after curing of the liquid crystal display element sealing compound is 350° C. or higher. 14, 15, 16 or 17, the sealant for liquid crystal display elements.
Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18. Liquid crystal display element.
A polyvalent hydrazide compound having two or more hydrazide groups represented by the following formula (5) in one molecule and having a sulfonyl group bonded to an aromatic ring.

In formula (5), * represents a binding position.
21. The polyhydrazide compound according to claim 20, which has a structure represented by the following formula (6).

In formula (6), R 1 to R 4 are each independently a group containing at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a nitrogen atom, a hydrogen atom, or , represents a linking group, and at least one of R 1 to R 4 is bonded to the hydrazide group represented by the formula (5).
22. The polyhydrazide compound according to claim 21, wherein at least one of R 1 to R 4 in the structure represented by formula (6) contains an amino group or a hydroxyl group.