KR101806152B1

KR101806152B1 - Novel thermal radical generator, method for producing the same, liquid crystal sealing agent, and liquid crystal display cell

Info

Publication number: KR101806152B1
Application number: KR1020127013344A
Authority: KR
Inventors: 마사노리 하시모토; 츠네토시 사카노; 나오미 하스미; 마키에 소네
Original assignee: 니폰 가야꾸 가부시끼가이샤
Priority date: 2009-11-17
Filing date: 2010-11-12
Publication date: 2017-12-07
Also published as: TWI482777B; JP5783606B2; CN102612521B; JPWO2011061910A1; CN104031082A; CN102612521A; TW201129574A; TW201437220A; TWI511974B; WO2011061910A1; KR20120085855A

Abstract

The present invention relates to a tetraphenyl ethane derivative represented by the following formula (1), a process for producing the same, a use of the tetraphenyl ethane derivative as a radical generator, a liquid crystal sealing agent comprising the tetraphenyl ethane derivative, and a thermosetting liquid crystal sealing When used in a liquid crystal sealing agent, the liquid crystal sealing agent obtained is free from liquid crystal contamination, has a long pot life, and is excellent in the formability of sealing, And the formation of the cell gap is also good. In formula (1), Y ¹ or Y ² each independently represents a hydrogen atom, a phenyl or a silicon atom, R ¹ to R ⁶ each independently represent a hydrogen atom or a straight or branched alkyl group having 1 to 4 carbon atoms X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group. However, R ¹ ~R ³ or R ⁴ ~R ^6, which respectively coupled to the Y ¹ or Y ² is a Y ¹ or Y ² is not present in the case of a hydrogen atom, and all of Y ^1, Y ² a hydrogen atom, Except the case.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel thermal radical generator, a method for producing the same, a liquid crystal sealing agent, and a liquid crystal display cell. BACKGROUND ART < RTI ID = 0.0 &

The present invention relates to a novel silylbenzopinacol, its use as a thermal radical generator, a liquid crystal sealing agent containing the same, and a liquid crystal display cell using the same.

Conventionally, azo compounds, organic peroxides, benzoins, benzoin ethers, acetophenones, benzophenones, etc. have been known and widely used as radical generating agents for curing radical polymerizable compounds by heating by heating .

An azo compound or an organic peroxide which is most likely to generate radicals due to thermal cleavage is used as a radical generating agent in products such as adhesives, sealants, gap formers and molding materials. However, since the radical generator accompanies generation of gas such as nitrogen or carbon dioxide at the time of generation of radicals, there is a concern that the characteristics of the above-mentioned product may be significantly impaired by the gas. For example, properties that may be damaged include a decrease in adhesive strength, a decrease in heat resistance, and a defective shape of a molded article. Other radical generators include benzoin, benzoin ethers, acetophenones, and benzophenol. In these cases, foaming at the time of heating is small, but there is a problem that the ability to generate radicals is poor and the desired performance (reactivity and curability) is not obtained.

Patent Document 1 discloses the use of benzopine coke as a thermal radical generator in order to cure a shaded portion not exposed to light in a system which is cured using both ultraviolet rays and heat. In Patent Document 2, it is disclosed that an initial putter type radical generator is effective in forming a molded article such as a contact lens, various lenses and dental materials, and examples thereof include benzopinacol. In Patent Document 3, benzopinacol is listed as a thermal radical generator used in a sealing agent for flat panel displays.

In Patent Documents 1 and 3, compounds further chemically modified benzopinacol are listed. It is described that the compound exerts further desired effects. However, it has not been reported that benzopinacol is a tertiary alcohol and that hydroxyl groups have insufficient reactivity due to the steric hindrance of the phenyl group to obtain stable derivatives.

As a field of use of a thermal radical generator, there is a liquid crystal sealing agent for a liquid crystal display cell.

In accordance with the enlargement of the liquid crystal display cell, the liquid crystal dropping method having higher mass productivity than that of the conventional method of manufacturing liquid crystal display cells by the liquid crystal vacuum injection method is introduced as a method of manufacturing liquid crystal display cells, (See Patent Document 4). The liquid crystal dripping method is a method in which a bank of a liquid crystal sealing agent is applied to a liquid crystal substrate (dummy sealing), and then a liquid sealing agent is applied on the outermost periphery (dummy sealing) The other liquid crystal substrate facing the other in the vacuum is laminated, the liquid crystal is sealed by opening to the atmospheric pressure, and the sealing portion is cured by UV irradiation and heating to complete the liquid crystal display cell. The liquid crystal sealing material used for sealing the liquid crystal in this manufacturing method is generally used as a liquid crystal sealing material for a photo thermosetting combination type, instead of a conventional thermosetting liquid crystal sealing material. The reason why the conventional thermosetting liquid crystal sealing agent (also referred to as a thermosetting liquid crystal sealing agent) is not used in the liquid dropping method is that when the liquid crystal dropping method is carried out using a conventional thermosetting liquid crystal sealing agent, heating is performed under vacuum decompression, The reason is that the thermal expansion of the liquid crystal at the time of heating and the viscosity decrease due to the heating of the liquid crystal sealing agent occur and the sealing is punctured and the liquid crystal can not be sealed.

A method of using a photo-thermal curing type liquid crystal sealing agent is a method in which a liquid crystal sealing agent is applied to a liquid crystal substrate by a dispenser or the like, a liquid crystal is dropped inside the bank and the other substrate facing the other in vacuum is stacked , The sealing part is irradiated with light such as ultraviolet light to make it harder and then the liquid crystal sealing agent is thermally cured at about 120 DEG C for about 1 hour to produce a liquid crystal cell.

However, in the case of the photo-thermal curing combination type, it is necessary to irradiate the liquid crystal sealing agent with light such as ultraviolet rays, but the following problems have been caused by the recent narrow frame of the liquid crystal cell.

That is, the liquid crystal sealing portion is shielded by the wiring or the black matrix, and the portion where the liquid crystal sealing agent is not irradiated with light is generated, and thus an uncured portion is generated. There is a problem that the uncured portion is inserted by the liquid crystal during the heat curing process or liquid crystal contamination occurs. For this reason, in designing the liquid crystal cell, there has been a restriction that the sealing agent should be designed so as to irradiate as much light as possible. In addition, since deterioration of the liquid crystal or the alignment layer due to ultraviolet irradiation is a problem, it is necessary to shield the liquid crystal portion with a light shielding mask during the ultraviolet irradiation process so that ultraviolet rays do not touch the liquid crystal. In addition, as the size of the liquid crystal glass substrate becomes larger, the size of the ultraviolet irradiating apparatus becomes larger, and the running cost of the ultraviolet irradiator is increased.

In view of the above, realization of a thermosetting liquid crystal sealing agent (thermosetting liquid crystal sealing agent for liquid crystal dropping process) capable of forming a liquid crystal display cell by thermal curing without requiring ultraviolet irradiation in the liquid crystal dropping method .

Up to now, a thermal curing type liquid crystal sealing agent for a liquid crystal dropping method has already been proposed. For example, Patent Document 5, the value obtained by dividing the number of hydrogen-bonding functional groups in one molecule with a molecular weight 3.5 × 10 ^-4 or more heat for a liquid crystal drop fill process which contains 3 to 40 parts by weight of a heat-curing agent based on 100 parts by weight of the curable resin A hardened liquid crystal sealing agent has been proposed. It is disclosed that low-liquid crystal contamination is caused by using this liquid crystal sealing agent. However, in the liquid crystal dropping method using the thermosetting liquid crystal sealing agent, there is a problem that the liquid crystal is leaked due to breakage of the bank of the liquid crystal sealing agent during the curing which is lowered in viscosity by the above-mentioned heating (the problem of the sealing puncture) When the component of the low viscosity liquid crystal sealing agent is heated to not less than the NI point (the temperature at which the transition from the isotropic phase to the liquid crystal phase), the liquid crystal is eluted into the liquid crystal which is more likely to flow than usual, It is hard to say that a serious problem has been solved sufficiently.

Further, in Patent Document 6, it is said that the liquid sealing agent added with the gelling agent can maintain an inner sealing funk and a sealing shape by a liquid dropping method of only thermal curing. However, the problem of contamination of the liquid crystal sealing agent in the liquid crystal upon thermal curing, which is a problem of the liquid crystal dropping method of thermosetting, has not been solved.

Patent Document 7 proposes a manufacturing method in which a liquid crystal sealing agent made of a thermosetting resin is applied, prebaking is performed, and then liquid dropping and vacuum bonding are performed. However, the resin composition of a specific liquid crystal sealing agent is not specified.

Patent Documents 8 and 9 propose a thermosetting liquid crystal sealing agent for a liquid crystal dropping method in which a pre-baking step is performed as a B-staged (semi-cured state) treatment. This method requires a B staging treatment at 80 占 폚 for 20 minutes, so that there is a drawback that the processing time becomes long. In addition, if the treatment temperature is raised to 100 ° C or higher, for example, to shorten the B staging treatment time for 20 minutes, the liquid crystal sealing agent as a base material is not preferable because the curing reaction proceeds.

Patent Document 7 proposes a liquid crystal sealing agent comprising a thermally curable radical generating agent, a thermosetting compound containing a compound having an unsaturated double bond, and a thermosetting agent having a mid-part type. In addition, there is described the production of a liquid crystal display element which irradiates part of the liquid crystal substrate with atmospheric pressure by UV light. However, there is no description about the production of a liquid crystal display element by only thermal curing without UV irradiation by vacuum pressure-bonding of the liquid crystal substrate.

As described above, there is no heat curing type liquid crystal drop sealing agent which solves all problems in the thermosetting sealing agent in the liquid crystal dropping method, and the liquid dropping method using only thermal curing is not yet realized.

In addition, in recent years, there has been a strong demand to increase the display area without increasing the external size of the substrate. For this purpose, a liquid crystal cell is designed such that a narrow frame for narrowing the outer periphery of the liquid crystal sealing portion and a liquid crystal sealing width is narrowed. As a result, a liquid crystal sealing agent which can form a narrow sealing width and is unlikely to be disturbed by a uniform sealing shape, and a liquid crystal sealing agent which exhibits a high bonding strength even if the sealing width is small. In addition, there is a demand for a liquid crystal sealing agent having a long pot life with little change in the application conditions of the liquid crystal sealing agent within the working time.

In recent years, in accordance with the spread of liquid crystal televisions and the like, the cell gap of the liquid crystal (the gap between the two substrates on which the liquid crystal is filled) is narrowed in order to improve the high-speed responsiveness of the liquid crystal to the reproduction of moving images. A liquid crystal sealing material which is easy to narrow cell gap upon vacuum bonding of a liquid crystal substrate is required.

In addition, with respect to the demand for the longevity of the liquid crystal cell, deterioration in the high-humidity conditioning of the liquid crystal sealing becomes a problem. A liquid crystal sealing agent having a small deterioration of the bonding strength of the liquid crystal sealing after the high temperature and high humidity test is required.

As described above, the liquid crystal dropping method of the thermosetting type is realized, the substrate is vacuum bonded, the sealing is not performed by heating, the liquid crystal is not contaminated, the bonding strength after bonding strength and humidity resistance test is strong, There is a demand for a thermosetting liquid crystal sealing agent for a liquid crystal dropping method which is excellent in properties, has a long pot life at room temperature, and is easily formed into a narrow cell gap.

Japanese Patent Application Laid-Open No. S57-53508 Japanese Patent Application Laid-Open No. H11-21304 Japanese Patent Application Laid-Open No. 2006-10870 Japanese Patent Application Laid-Open No. H08-20627 Japanese Patent No. 3955038 Japanese Patent No. 3976749 Japanese Patent Application Laid-Open No. 2005-92043 Japanese Patent Application Laid-Open No. 2007-199710 Japanese Patent Application Laid-Open No. 2007-224117

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and a first object of the present invention is to develop a new thermal radical generating agent which is not foaming at the time of heating but is more highly active.

A second object of the present invention is to provide a thermosetting liquid crystal sealing agent for a liquid crystal dropping method which does not require ultraviolet irradiation. In addition, a thermosetting liquid crystal sealing agent for a liquid crystal dropping method which has low stain on liquid crystal contamination, strong adhesive strength after adhesion and humidity resistance test, excellent sealing linearity, long pot life at room temperature, and easy narrow cell gap (Also referred to as a thermosetting liquid crystal sealing agent for public methods).

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive studies to solve the above problems and found that by silylating at least one hydroxyl group of benzopinacol which may have a substituent on a benzene ring, The present inventors have found that a thermosetting liquid crystal sealing agent for a liquid crystal dropping method as described above is obtained by using a heat radical generating agent and a thermal radical generating agent.

That is, the present invention relates to the following (1) to (20).

(1) a tetraphenyl ethane derivative of the formula (1 '):

Wherein each of Y ^{1 '} and Y ^2' independently represents a hydrogen atom or a silicon atom, each of R ¹ to R ⁶ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group. Stage, Y ^{1 'or} Y ^2' each bonded R ¹ ~R ³ or R ⁴ ~R ⁶ is Y ^{1 'or} Y ^2' is a hydrogen atom, is absent, and Y ^{1 'and} Y ^2' to the Except that the case where Y ^{1 '} and Y ^2' are silicon atoms, all of R ¹ to R ⁶ are methyl groups, and all of X ^{1 to} X ⁴ are hydrogen atoms, except when hydrogen is a hydrogen atom.

(2) In the above-mentioned (1), when any one of Y ^{1 '} and Y ^{2' in} the formula (1 ') is a hydrogen atom and the other is a silicon atom and a silicon atom, R ¹ R ² R ³ Y ^{1 '-,} or ^{R 4 R 5 R 6 Y 2} ' - di silyl group and, X (straight chain or branched alkyl having 1 to 4 carbon atoms) silyl group, or a tri (straight chain or branched alkyl having 1 to 4 carbon atoms) Tetraphenyl ethane derivatives in which the tannin of ^{1 to} X ⁴ is a hydrogen atom.

(3) In (1) or (2), when any one of Y ^{1 '} and Y ^2' is a hydrogen atom and the other is a silicon atom in the formula (1 ' ¹ R ² R ³ Y ^{1 '} - or R ⁴ R ⁵ R ⁶ Y ^2' - is trimethylsilyl, triethylsilyl or t-butyldimethylsilyl, and all of X ^{1 to} X ⁴ are hydrogen atoms. .

(4) In any one of (1) to (3) above,

A tetraphenyl ethane derivative of 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane represented by the following formula (2).

(5) A process for producing a tetraphenyl ethane derivative represented by the following formula (1): (a) a tetraphenyl ethane derivative represented by the following formula (1); (b) one or both of an epoxy resin or (meth) acrylic acid adduct of an epoxy resin; A thermosetting liquid crystal sealing agent for a liquid crystal dropping method comprising:

Wherein each of Y ¹ and Y ² independently represents a hydrogen atom, a phenyl group, or a silicon atom, R ¹ to R ⁶ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom. However, in the case of Y ^1, or R ¹ ~R ³ or R ⁴ ~R ⁶ is Y ¹ or Y ² are hydrogen atoms bonded to each Y ² is absent, and all of Y ¹ and Y ² a hydrogen atom, Except the case.

(6) The liquid crystal composition according to the above (5), wherein (a) the tetraphenyl ethane derivative of the formula (1) is a tetraphenyl ethane derivative described in any one of (1) to (4) .

(7) The liquid crystal sealing agent according to (5) or (6) above, wherein (a) the tetraphenylethane derivative of the formula (1) is a solid powder having an average particle size of 5 탆 or less.

(8) The liquid crystal sealing agent according to any one of (5) to (7), wherein the curing agent is a latent curing agent having a melting point or softening point of 100 ° C or higher.

(9) The liquid crystal sealing agent according to any one of (5) to (8), wherein (d) the inorganic filler is alumina and / or silica.

(10) The liquid crystal sealing agent according to any one of (5) to (9) above, wherein (d) the inorganic filler has an average particle diameter of 10 to 2000 nm.

(11) The liquid crystal sealing agent according to any one of (5) to (10), further comprising (e) a curing accelerator.

(12) The liquid crystal sealing agent according to any one of (5) to (11), further comprising (f) a coupling agent.

(13) The liquid crystal composition according to any one of (5) to (12) above, wherein (a) the tetraphenylethane derivative of the formula (1) is contained in an amount of 0.1 to 10% by mass based on the total amount of the liquid crystal sealing agent, (b) (Meth) acrylic acid adduct of an epoxy resin in an amount of 30 to 75 mass% based on the total amount of the liquid crystal sealing agent, (c) 5 to 60 parts by mass of the thermosetting agent relative to 100 parts by mass of the component (b) and d) an inorganic filler in an amount of 1 to 30% by mass based on the total amount of the liquid crystal sealing agent.

(14) In any one of (5) to (13) above, (a) in formula (1), one of Y ¹ and Y ² is a hydrogen atom and the other is a silicon atom, , R ¹ R ² R ³ Y ¹ - or R ⁴ R ⁵ R ⁶ Y ² - is a ^divalent (straight-chain or branched alkyl) silyl group having 1 to 4 carbon atoms, or tri (linear or branched alkyl having 1 to 4 carbon atoms) a silyl group, both of X ¹ ~X ⁴ is a hydrogen atom, a tetraphenyl ethane derivative, (b) an epoxy resin or an epoxy resin (meth) acrylic add any water one or a combination of the two, (c) a melting point or softening point as a thermal curing agent (D) an inorganic filler, (e) a curing accelerator, or (f) a coupling agent, wherein the liquid crystal sealing agent is a liquid crystal sealing agent.

(15) A liquid crystal display cell sealed with a cured product of the liquid crystal sealing agent according to any one of (5) to (14).

(16) A radical generator comprising a tetraphenyl ethane derivative of the formula (1) as described in (5) as an active ingredient.

(17) Use of the tetraphenyl ethane derivative of the formula (1) as the radical generator according to the above (5) for producing a thermosetting liquid crystal sealing agent as described in (16) above.

(18) A cured product obtained by thermally curing a radical curable resin composition comprising the tetraphenyl ethane derivative of the formula (1) described in (5) above.

(19) A process for producing a tetraphenyl ethane derivative of the following formula (1 ') for reacting a benzopyran of formula (3) with a silylating agent:

X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group,

Y ^{1 '} or Y ^2' each independently represents a hydrogen atom or a silicon atom, and R ¹ to R ⁶ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Stage, Y ¹ R ^1, which respectively coupled to the ^'or Y ^2' ~R ³ or R ⁴ ~R ⁶ is Y ^{1 'or} Y ^2' is Y ^1, Y ^2, and further when the hydrogen atoms is not present, ^"in all cases except a hydrogen atom.

(20) In (1), when any one of Y ^{1 '} and Y ^{2' in} the formula (1 ') is a hydrogen atom and the other is a silicon atom, R ¹ to R ³ or R ⁴ to R ⁶ each independently represent a straight-chain or branched alkyl group having 1 to 4 carbon atoms.

The tetraphenyl ethane derivative (also referred to as a benzopinacole derivative) of the formula (1) used in the present invention is useful as a thermal radical generator, and it is possible to accelerate the reaction speed without foaming at the time of heating. Therefore, it can be widely used for various uses such as adhesives, sealants, gap formers, molding materials and the like as a thermal radical generating agent which does not cause deterioration of physical properties due to foaming, , Adhesive strength, shape stability, etc.) can be obtained. In particular, it is excellent as a thermal radical generator for a thermosetting liquid crystal sealing agent used in a liquid dropping method.

The thermosetting liquid crystal sealing agent using the tetraphenyl ethane derivative of the formula (1) used in the present invention as a thermal radical generating agent is a thermosetting liquid crystal sealing agent for liquid crystal dripping method which does not require ultraviolet irradiation to the liquid crystal sealing part Hereinafter also referred to as the liquid crystal sealing agent of the present invention). Since the liquid crystal sealing agent is low in stain on liquid crystal, has strong adhesive strength after the bonding strength test and humidity resistance test, has excellent sealing linearity, and has excellent properties such as long life at room temperature, . As a result, a liquid crystal display cell with high yield, high reliability, and high quality can be manufactured. The liquid crystal display cell of the present invention sealed with a cured product of the liquid crystal sealing agent of the present invention is free from display defects due to liquid crystal contamination, and is excellent in adhesiveness and moisture resistance reliability.

The tetraphenyl ethane derivative of the above formula (1 ') is a novel compound synthesized by the present inventors.

1 is an NMR (proton) spectrum (solvent: DMSO-d6) of 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane of the present invention.

Hereinafter, the present invention will be described in detail.

In the following description, for convenience, the formula (1) is described, but any explanation except for the case where the compound does not fall within the range of the formula (1 ') substitutes the formula (1) , The same applies to the formula (1 '). In addition, it is assumed to be equally applicable, except that, by also in the description of Y ¹ and Y ^2, and replacing each with a Y ^{1 'and} Y ^2', that are outside the scope of Y ^{1 'and} Y ^2'.

In the formula (1) of the present invention, Y ¹ and Y ² each independently represent a hydrogen atom, a phenyl group or a silicon atom, and at least one of them is a group other than a hydrogen atom. Preferred is a case where one side is a hydrogen atom and the other side is a silicon atom.

Examples of the straight chain or branched alkyl group having 1 to 4 carbon atoms (hereinafter simply referred to as C1 to C4 alkyl group) in R ¹ to R ⁶ in the formula (1) of the present invention include methyl, ethyl, n- Propyl, i-propyl, t-butyl and the like. Examples of the halogen in X ^{1 to} X ⁴ include a fluorine atom, a chlorine atom and a bromine atom.

When Y ¹ or Y ² in the formula (1) is a group other than a hydrogen atom, R ¹ R ² R ³ Y ¹ - or R ⁴ R ⁵ R ⁶ Y ² - is a phenyl group or a phenyl group substituted with 1 to 3 C1- More preferably a di C1 to C4 alkylsilyl group or a tri-C1 to C4 alkylsilyl group, more preferably a di C1 to C4 alkylsilyl group or a tri-C1 to C4 alkylsilyl group, to be.

In the straight or branched alkylsilyl group having 1 to 4 carbon atoms in the di or tri carbon atom in R ¹ R ² R ³ Y ¹ - and R ⁴ R ⁵ R ⁶ Y ² - in the formula (1), two or three carbon atoms C4 alkyl groups may be the same or different from each other, and examples of the silyl group include di-C1-C4 alkylsilyl groups such as dimethylsilyl, diethylsilyl and methylethylsilyl, or trimethylsilyl, triethylsilyl, dimethylethyl Silyl, and t-butyldimethylsilyl; . Of these, a tri-C alkylsilyl group is preferable, and a trimethylsilyl group is more preferable.

X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group, and preferably all of X ¹ to X ⁴ are hydrogen atoms.

Preferred compounds in the tetraphenyl ethane derivatives of formula (1) include 1-hydroxy-2-di or tri (C1-C4 alkyl) siloxy-1,1,2,2-tetraphenylethane or 1,2- Bis (di- or tri- (C1-C4 alkyl) siloxy} -1,1,2,2-tetraphenyl ethane and 1-hydroxy-2-di or tri More preferably 1,1,2,2-tetraphenylethane, and more preferably 1-hydroxy-2-tri (C1-C4 alkyl) siloxy-1,1,2,2-tetraphenylethane.

The di or tri (C1-C4 alkyl) siloxy in the tetraphenyl ethane may have the same or different 2 or 3 alkyl groups on the silyl group. Examples of the tri (C1-C4 alkyl) siloxy include trimethylsiloxy, triethylsiloxy, t-butyldimethylsiloxy, and the like.

Specific examples of the tetraphenyl ethane derivative include 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) Bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1 -hydroxy-2-trimethylsiloxy- 1,1,2,2-tetraphenyl ethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1 -hydroxy-2-t-butyldimethylsiloxy- 1,1,2,2-tetraphenyl ethane. Preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane.

Among them, in the present invention, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1 -hydroxy-2-triethylsiloxy- Tetraphenyl ethane or 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane is more preferable and 1-hydroxy-2-trimethylsiloxy- More preferred are 1,1,2,2-tetraphenyl ethane.

The tetraphenyl ethane derivative of the formula (1) of the present invention is characterized by a structure in which benzopinacol of the formula (3) is silylated with various silylating agents.

The tetraphenyl ethane derivative of the formula (1) of the present invention can be obtained by synthesizing a benzopinacol derivative of the formula (3) and various silylating agents by heating in a basic catalyst such as pyridine.

The silylating agent may be any one as long as it can di-C1-C4 alkylsilylation or tri-C1-C4 alkylsilylation or phenyldi C1-C4 alkylsilylation, and tri (C1-C4 alkyl) silylation agent is preferable. Preferred are trimethylsiloxane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), triethylsilylating agent , Triethylchlorosilane (TECS) as t-butyldimethylsilylating agent and t-butyldimethylsilane (TBMS) as t-butyldimethylsilylating agent.

These reagents are readily available from markets such as silicone derivatives manufacturers. The reaction amount (silylation equivalent) of the silylating agent is preferably 1.0 to 5.0 times equivalent to 1 equivalent of the hydroxyl group of the benzopinacol of the formula (3). More preferably 1.5 to 3.0 times equivalent. If the amount is too small, the reaction efficiency is poor, and the reaction time is prolonged, thereby promoting pyrolysis. If it is too much, separation becomes worse when it is collected, or purification becomes difficult.

Examples of the basic catalyst include pyridine, triethylamine, and the like. The basic catalyst has an effect of trapping hydrogen chloride generated in the reaction and keeping the reaction system basic, or removing hydrogen atoms in the hydroxyl group to further promote the reaction. The amount to be used may be equal to or more than 0.5 times equivalent to the equivalent amount of the basic group with respect to 1 equivalent of the hydroxyl group of the target compound and may be used as a solvent. Usually, the equivalent of the basic group of the basic catalyst is 1 to 5 times equivalent to 1 equivalent of the hydroxyl group of the target compound.

As the solvent, non-polar organic solvents such as hexane, ether, and toluene are excellent because they are not involved in the reaction. Also preferred are polar solvents such as pyridine, dimethylformaldehyde (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF) and acetonitrile. It is preferable that the weight concentration of the solute is 5 to 40 mass%. More preferably 10 to 30% by mass. If the amount is too small, the reaction is delayed and the decomposition by heat is promoted, and the yield is reduced. If too much, the number of by-products increases and the yield decreases.

When the silyl group is introduced into one of the hydroxyl groups of the benzopyran of formula (3), the reaction temperature is preferably 80 ° C or lower, and the reaction time is preferably 2.5 hours or less, preferably 2 hours or less. Benzopinacol derivatives such as benzopinacol of the formula (3) or the desired compound produced are preferably reacted at a low temperature in order to cause thermal decomposition by heating, but because of the lack of reactivity due to the tertiary alcohol, In a short period of time to obtain a target product at a high yield. Considering the reaction efficiency and the like, about 50 to 80 캜 is preferable. The reaction time is about 30 minutes to 2.5 hours, preferably about 30 minutes to 2 hours.

When a silyl group is introduced into both of the hydroxyl groups of the benzopinacol of the formula (3), a higher temperature, for example, a temperature of about 75 to 100 캜 is preferable, but the yield is considered to be lowered.

The tetraphenyl ethane derivative of the formula (1) of the present invention can be used as a radical generating agent. Specifically, it can be used in various fields as a heat radical generator and a photo radical generator, and it is particularly preferable to use it as a heat radical generator in the present invention.

The thermal radical generator of the present invention can also be used for applications that are difficult to achieve with other photoradical generators. For example, irradiation with hardening or strong energy of a portion not exposed to light can be used for hardening of a problematic portion. Specifically, as a thermal radical generating agent in a sealing agent for precision instruments, as a thermal radical generating agent for curing an area in which a low-molecular substance concerned about decomposition coexists, and as a thermal radical generating agent for organic synthesis by a thermal reaction It can be used as a generator. In addition, since the thermal radical generating agent of the present invention does not accompany foaming at the time of radical generation and does not impair the curing rate even in a small amount, it is expected that the cured product is maintained in shape and improved in physical properties. In the present invention, the amount of the tetraphenyl ethane derivative of the above formula (1) used as the radical generator may vary depending on the kind of the polymerized monomer to be cured and the field of use, and the amount of the tetraphenylethane derivative may be appropriately selected.

One preferred field of use of the thermal radical generator of the present invention is its use as a thermal radical generator in a radical curable resin composition. In this case, the content of the thermal radical generator (tetraphenylethane derivative of the formula (1)) of the present invention relative to the total amount of the composition is not particularly limited, but is usually about 0.1 to 10 mass%. The remainder is a radical polymerizable resin and an additive that can be included if necessary. The resin composition is thermally cured to obtain a cured product of the resin composition. The cured product is excellent in transparency since it does not cause haze due to foaming, and is excellent in adhesiveness, moisture resistance adhesion, and the like . Examples of the radical curable resin include an epoxy resin and a (meth) acrylic resin. Particularly, as a useful radical curable resin composition, a thermosetting sealing agent can be exemplified, and among these, a thermosetting liquid crystal sealing agent for a liquid crystal dropping method is most suitable.

(B) an epoxy resin and / or a (meth) acrylic acid adduct of an epoxy resin; (c) a thermosetting liquid crystal sealing agent of a liquid crystal dropping method; A hardening agent, and (d) an inorganic filler.

The thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains (a) a tetraphenyl ethane derivative of the formula (1) as a thermal radical generator in order to improve curability. In order to simplify the tetraphenyl ethane derivative of the formula (1) below, the component (a) or the thermal radical generator (a) is also described.

Generally, a thermal radical generator refers to a compound which generates dissociation of radicals by heating, and examples thereof include azo compounds, organic peroxides, benzoins, benzoin ethers, acetophenones, and benzopinacols. However, when an azo compound or an organic peroxide is generated by heating, nitrogen, carbon dioxide, or the like is generated and foamed. As a result, bubbles are contained in the cured product, which causes deterioration of the cured properties and the bonding strength. In addition, benzoin derivatives, benzopinacol, and the like do not foam during heating. However, when the temperature of the heat curing temperature of the sealing agent usable in the production of the liquid crystal panel is about 90 to 130 占 폚, There is a problem that the desired degree of curing is not obtained.

Therefore, the inventors of the present invention have conducted various investigations and found that by chemically modifying benzopinacol, a more active and less liquid-contaminated thermal radical generator is obtained. Further, it has been found that a benzopinacol derivative in which at least one of the hydroxyl groups of pinacol is an ether bond is more preferable from the viewpoint of ease of synthesis. Examples of the ether linkage include methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, phenyl ether group and silyl ether group. Of these, a phenyl ether group or a silyl ether group is preferable from the standpoint of activity and the tetraphenyl ethane derivative of the above formula (1) is more preferable.

Preferred tetraphenyl ethane derivatives (a) of formula (1) for use in the present invention include 1-hydroxy-2-di or tri (C 1 -C 4 alkyl) siloxy-1,1,2,2- Di (C1 to C4 alkyl) siloxy} -1,1,2,2-tetraphenyl ethane, and 1-hydroxy-2-di or tri Siloxyl-1,1,2,2-tetraphenyl ethane is more preferable, and more preferable is 1-hydroxy-2-tri (C1-C4 alkyl) siloxy-1,1,2,2-tetra Phenyl ethane. Specific examples of the compound are as described above.

It is preferable that the thermal radical generator (a) (tetraphenyl ethane derivative (a) of formula (1)) is uniformly dispersed with a narrow particle size. If the average particle diameter is too large, it becomes a cause of defects such as a failure to form a gap when the upper and lower glass substrates are laminated during the production of the liquid crystal cell with a narrow gap. Therefore, the thickness is preferably 5 탆 or less, more preferably 3 탆 Or less. The particle diameter of the component (a) may be made thinner without limitation, but the lower limit thereof is usually about 0.1 탆 in average particle diameter.

The content of the heat radical generating agent (a) in the liquid crystal sealing agent of the present invention is usually 0.1 to 10 mass%, preferably 0.3 to 7 mass%, more preferably 0.5 (mass%) based on the total amount of the liquid crystal sealing agent To 5% by mass. If the content is too small, the curing property deteriorates and a sealing puncture occurs. When the content is too large, the liquid crystal staining property tends to become strong.

In the present invention, as long as the effect of the present invention is achieved, a radical generating agent other than the component (a) may be used in combination. In general, it is preferable to use the component (a) alone as the radical generating agent.

The epoxy resin and / or the (meth) acrylic acid adduct (b) of the epoxy resin contained in the thermosetting liquid crystal sealing agent for liquid crystal dropping method of the present invention is used as a curable resin. Herein, "(meth) acryl" means "acryl" and / or "methacryl". (B) of the epoxy resin and / or the (meth) acrylic acid adduct of the epoxy resin are all preferably low in stainability and solubility in liquid crystals, and low in resin viscosity.

Preferable examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, ethylene oxide addition bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy Resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, resorcinidiglycidyl ether, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy Resin, epoxy resin of Hai Danto dolman type, epoxy resin of isocyanurate type, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin having triphenol methane skeleton, diglycidyl And diglycidyl ether compounds of other bifunctional alcohols. These epoxy resins may be used alone or in combination of two or more. Among them, more preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, ethylene oxide addition bisphenol S type epoxy resin and resorcin sodium glycidyl ether from the viewpoint of liquid crystal staininess and viscosity, Diesters are preferred.

(Meth) acrylic acid adduct of the epoxy resin (hereinafter, also referred to as "(meth) acrylated epoxy resin" for convenience) is a compound obtained by the reaction of an epoxy resin with (meth) acrylic acid, (Meth) acrylic acid, or a compound in which an epoxy group of less than the equivalent amount is reacted with (meth) acrylic acid to intentionally leave an epoxy group (hereinafter also referred to as a partial (meth) acrylated epoxy resin).

As the (meth) acrylated epoxy resin, a compound having two or more functional (meth) acryloyl groups is preferable. The ratio of the epoxy group to the (meth) acryloyl group in the part (meth) acrylated epoxy resin is not limited, and is appropriately selected from the viewpoints of process suitability and liquid crystal stain resistance.

In the present invention, usually, the amount of (meth) acrylic acid added with (meth) acrylic acid in a proportion of 50 to 100%, preferably 70 to 100%, and more preferably 80 to 100% based on the total epoxy groups contained in the epoxy resin ) Acrylated epoxy resin is preferable. In general, acrylic acid is often used because of its low cost in (meth) acrylic acid. Therefore, it is preferable to use a compound obtained by adding acrylic acid to the epoxy group of the epoxy resin.

The epoxy resin to be used as a raw material of the (meth) acrylated epoxy resin is not particularly limited, but an epoxy resin having two or more functionalities is preferable.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, ethylene oxide addition bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type Epoxy resin, bisphenol F novolak type epoxy resin, resorcinidiglycidyl ether, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, , Isocyanurate type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin having triphenol methane skeleton, diglycidyl ether compound of other bifunctional phenols, other 2 And diglycidyl ether compounds of functional alcohols.

Preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins and resorcinediglycidyl ethers, among which resorcinediglycidyl ether is preferable.

Accordingly, the (meth) acrylated epoxy resin is preferably a (meth) acrylated epoxy resin obtained by the reaction of (meth) acrylic acid with at least one member selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin and resorcin diglycidyl ether. ) Acrylate epoxy resin is preferable, and a (meth) acrylated epoxy resin obtained by the reaction of resorcine diglycidyl ether with (meth) acrylic acid is more preferable.

As the (meth) acrylated epoxy resin, an acrylated epoxy resin obtained by reaction of an epoxy resin with acrylic acid is preferable from the viewpoint of curability. More preferably at least one member selected from the group consisting of an acrylic acid adduct of a bisphenol A type epoxy resin, an acrylic acid adduct of a bisphenol F type epoxy resin, and an acrylic acid adduct of a resorcinidiglycidyl ether.

The above-mentioned (meth) acrylated epoxy resins may be used alone or in combination of two or more.

In a preferred embodiment, the preferred (meth) acrylated epoxy resin occupies the entire amount of the (meth) acrylated epoxy resin in the liquid crystal sealing agent.

The content of the epoxy resin and / or the (meth) acrylated epoxy resin (b) (hereinafter also simply referred to as the curable resin (b)) in the liquid crystal sealing agent of the present invention is usually from 30 to 75 Mass%, preferably 40 to 65 mass%. When the content is too small, the reaction at the time of thermal curing is delayed, and the bank of the sealing agent at the time of making the liquid crystal cell by the liquid crystal dropping method causes a sealing puncture by the thermal expansion of the liquid crystal and the heating low viscosity of the sealing agent. If the content is too large, sufficient adhesive strength is not obtained.

As the curing resin (b), a mode in which both an epoxy resin and a (meth) acrylated epoxy resin are used is one of preferable forms in the sealing agent of the present invention.

When the epoxy resin and the (meth) acrylated epoxy resin are used in combination, the content of the epoxy resin in the curable resin (b) is usually 3 to 40 mass%, preferably 3 to 40 mass%, based on the total amount of the curable resin (b) More preferably about 3 to 30 mass%, more preferably about 5 to 30 mass%, and still more preferably 8 to 30 mass%. In some cases, the amount is preferably 5 to 20% by mass, and more preferably 8 to 15% by mass. The remainder is a (meth) acrylated epoxy resin. Specifically, the content of the (meth) acrylated epoxy is 60-97 mass%, preferably 70-95 mass%, and more preferably 70-92 mass% with respect to the total amount of the curable resin (b). If the content of the epoxy resin is too small, the bonding strength becomes weak. If the content of the epoxy resin is too large, the curing will be delayed and the sealing puncture tends to occur easily.

The thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains a thermosetting agent (c). As the thermosetting agent (c), all conventionally used thermosetting agents may be used, but in the present invention, a thermosetting agent having a potential (hereinafter also referred to as a latent curing agent) is preferable. The latent curing agent is a compound having a melting point or a softening point of 100 占 폚 or more at room temperature and does not react with the resin component at room temperature and does not exhibit the function as a curing agent but is usually heated to 100 to 150 占 폚, Refers to a resin that reacts with the resin component by slowly dissolving or melting by about 130 ° C to exhibit an action as a curing agent.

The melting point or softening point in the present invention was measured by thermal analysis using a differential scanning calorimeter (DSC). Specifically, a differential scanning calorimeter (EXSTAR6000, manufactured by Seiko Instruments Inc.) was used and the temperature was measured at a rate of 5 DEG C / min.

Examples of the latent curing agent include polyhydrazide compounds, polyamine compounds, imidazole derivatives, urea derivatives, and the like. Preferably a polyhydrazide compound, and is a compound having two or more hydrazide groups in the molecule. Di-tetrahydrazide compounds are preferable, and di- or trihydrazide compounds are more preferable.

Examples of the polyhydrazide compound include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, And examples thereof include dihydrazide, dodecanedioididazide, hexadecanediohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid Dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene dihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, Dihydrazide such as trihydrazide, pyromellitic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide and 1,3-bis (hydrazinocarbonoethyl) -5-isopropyl hydantoin The skeleton, preferably A hydrazide compound having a valine hydantoin skeleton (a skeleton in which a carbon atom of a hydantoin ring is replaced with an isopropyl group); Tris (3-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinobonylpropyl) isocyanurate, bis (Hydrazinocarbonyl C1-C3 alkyl) isocyanurate, and these may be used alone or in combination of two or more. Bis or tris (hydrazinocarbonyl C1 to C3 alkyl) isocyanurate is one of the preferred di- or trihydrazide compounds.

Among these polyhydrazide compounds, preferred are di- or trihydrazides of di- or tricarboxylic acids, and more specifically, dihydrazides of C4-C8 aliphatic or aromatic dicarboxylic acids, other than carbon of carboxylic acids, Bis or tris (hydrazinocarbonyl C1-C3 alkyl) isocyanurate, and the like. More preferably at least one selected from the group consisting of dihydrazide of C4 to C8 alkylenedicarboxylic acid, phthalic acid dihydrazide, and tris (hydrazinocarbonyl C1 to C3 alkyl) isocyanurate.

Preferred examples of the polyhydrazide include adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropyl hydantoin, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylmethyl) isocyanurate, tris Ethyl) isocyanurate.

More preferred are adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide and tris (2-hydrazinocarbonylethyl) isocyanurate.

It is preferable that the heat curing agent (c) is uniformly dispersed with a narrow particle size in order to obtain a fast curing latent curing agent. If the average particle diameter is too large, a gap can not be formed well when the upper and lower glass substrates are laminated in manufacturing a liquid crystal cell having a narrow gap. Therefore, the particle diameter is preferably 4 탆 or less, and more preferably 3 탆 or less. The particle size was measured by a laser diffraction / scattering type particle size distribution analyzer (dry type) (LMS-30 manufactured by Seishin KK). Furthermore, since the average particle diameter is too small, aggregation tends to occur. Therefore, it is preferable to prepare the particles so as not to be extremely small (for example, 0.1 탆 or less).

The content of the thermosetting agent (c) in the liquid crystal sealing agent of the present invention is usually about 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the curable resin (b) which is an epoxy resin and / or a (meth) Is from 10 parts by mass to 40 parts by mass. When the amount of the thermosetting agent (c) is less than 5 parts by mass, the thermosetting reaction becomes insufficient and the adhesive force and the glass transition point are lowered. On the other hand, if the amount of the thermosetting agent (c) is more than 60 parts by mass, the curing agent remains and the adhesive strength is deteriorated, and the pot life also deteriorates.

The thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains an inorganic filler (d). Examples of the inorganic filler (d) include metal oxides such as alumina, silica (spherical silica or fumed silica), talc, clay, bentonite, organic bentonite, barium titanate, titanium oxide, cobalt oxide, magnesium oxide, , Carbonates such as calcium carbonate and magnesium carbonate, sulphates such as barium sulfate and calcium sulfate, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and silicates such as calcium silicate, aluminum silicate and zirconium silicate. These may be used alone or in combination of two or more. Among these inorganic fillers, alumina and / or silica is particularly preferable.

The average particle diameter of the inorganic filler (d) is preferably 3 탆 or less.

If the average particle diameter is too large, there is a problem in forming a gap at the time of bonding the upper and lower glass substrates at the time of manufacturing the liquid crystal cell. The lower limit of the average particle diameter of the inorganic filler (d) is usually about 0.01 mu m.

The content of the inorganic filler (d) in the liquid crystal sealing agent of the present invention is usually 1 to 30 mass%, preferably 2 to 20 mass%, and more preferably 3 to 15 mass%. When the content is too small, the adhesive strength to the glass substrate is lowered. When the content of the filler is too large, the viscosity is too high and the coating property is deteriorated.

The liquid crystal sealing agent of the present invention contains a curing accelerator (e) in order to accelerate the curing property of the thermosetting reaction.

The curing accelerator (e) is not particularly limited as long as it can accelerate the thermal curing reaction at the time of heating, has low staining property to the liquid crystal, and does not deteriorate the pot life of the liquid crystal sealing agent at room temperature storage.

Examples thereof include polyvalent carboxylic acids having an isocyanurate skeleton, epoxy resin amine adduct water, imidazole derivatives, urea derivatives and the like. These may be used alone or in combination of two or more. Preferred curing accelerators include urea curing accelerators or polyacarboxylic acid curing accelerators containing an isocyanurate skeleton. Concretely, an aliphatic dimethylurea (trade name: UCAT3503N San-Apro Ltd.) (a compound in which a methyl group and two dimethylurea groups are successively substituted on a cyclohexane ring), aromatic dimethylurea (trade name: UCAT3502T San-Apro Ltd .) (A compound in which two dimethylurea groups are substituted at positions 2 and 3 of toluene), and tris (carboxy C1-C3 alkyl) isocyanurate. Examples of tris (carboxy C1-C3 alkyl) isocyanurate include tris (1-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, and the like. Among them, tris (3-carboxypropyl) isocyanurate is preferable.

The curing accelerator (e) is preferably uniformly dispersed with a narrow particle size in order to make it a latent curing accelerator for rapid curing. If the average particle diameter is too large, it becomes a factor of defects such that gap formation is not performed well when the upper and lower glass substrates are laminated in manufacturing a liquid crystal cell of a narrow gap. Therefore, the average particle diameter is preferably 4 탆 or less, and more preferably 3 탆 or less. The lower limit of the average particle diameter is usually about 0.1 mu m.

The content of the curing accelerator (e) in the liquid crystal sealing agent of the present invention is preferably 0.5 to 15 mass%, more preferably 1 to 8 mass%, based on the total amount of the liquid crystal sealing.

If the content is too small, the curing property is deteriorated to cause a sealing puncture. If the content is too large, the storage stability at room temperature and the linearity of sealing are deteriorated.

To the liquid crystal sealing agent of the present invention, a coupling agent (f) may be added to improve the bonding strength. There is no particular limitation on the coupling agent (f).

Examples of the coupling agent (f) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 Aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamine) ethyl) 3-aminopropyltri Silane coupling agents such as methoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane; (Dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neo alkoxy tri (meth) acrylate, (pN- (beta -aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neo Zirconium-based coupling agents such as alkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, and ammonium zirconium carbonate; Aluminum-based coupling agents such as Al-acetylacetonate, Al-methacrylate, and Al-propionate; These may be used alone or in combination of two or more.

Of these coupling agents, silane coupling agents are preferable, and amino silane coupling agents or epoxy silane coupling agents are more preferable.

By using the coupling agent, a liquid crystal sealing agent having excellent moisture and moisture reliability and less decrease in adhesive strength after moisture absorption is obtained. When the liquid crystal sealing agent of the present invention contains the coupling agent, the content thereof is about 0.05 to 3% by mass.

The liquid crystal sealing agent of the present invention may contain a polythiol compound (g) in order to improve the hardenability. The polythiol compound is preferably a compound having two or more thiol groups in the molecule, and examples thereof include methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimer (Mercaptoethanol) sulfone, 1,6-dimercaptohexane, 1,6-dimercaptohexane, 1,1-dimercaptoheptane, (2-mercaptoethylthio) ethane, 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2- Dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4- Dimercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, -Tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylol (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, Dimercaptocyclohexane, dipentaerythritol hexacis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol tetra (2-mercaptoacetate), 1,2-dimercaptobenzene, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, , 3-butanediol, hydroxymethyl-tris (mercaptoethylthiomethyl) methane, hydroxyethylthiomethyl-tris (mercaptoethylthio (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate), octanediol bis (3-mercaptopropionate) (4-mercaptopropionate), ethylene glycol bis (4-mercaptobutyrate), propylene glycol bis (4-mercaptobutyrate), butanediol bis (4-mercaptobutyrate) , Trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), ethylene glycol bis (6-mercaptovalerate), propylene glycol But are not limited to, bis (6-mercaptovalerate), butanediol bis (6-mercaptovalerate), octanediol bis (6-mercaptovalerate), trimethylolpropane tris 1,6-hexanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 4,4'-bis (mercaptomethyl) phenyl sulfide, 2 , 2,4'-tri (mercaptomethyl) phenyl sulfide, 2,2 ', 4,4'-tetra (mercaptomethyl) phenyl sulfide, , 1,3,5-tris [2- (3-mercaptopropionyloxy) ethyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) (1H, 3H, 5H) -triene, pentaerythritol tetrakis (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ) And 1,4-bis (3-mercaptobutyryloxy) butane. These may be used alone or in combination of two or more.

Of these polythiol compounds, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) 1,3,5-tris [2- (3-mercaptopropionyloxy) ethyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) , 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, pentaerythritol tetrakis (3-mercaptobutyrate) More preferably 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-1,3,5-triazine having a secondary thiol structure from the viewpoint of liquid crystal staining property and storage stability at room temperature, 2,4,6 (1H, 3H, 5H) -thione and pentaerythritol tetrakis (3-mercaptobutyrate) are particularly preferable.

When the polythiol compound (g) is contained in the thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention, its content is usually 0.1 to 10% by mass, preferably 0.3 to 5% by mass. If the content is too small, the curing property is deteriorated and the sealing puncture tends to occur. If the content is too large, the storage stability at room temperature tends to deteriorate.

The organic filler (h) may be added to the thermosetting liquid crystal sealing agent for liquid crystal dropping method of the present invention within a range not affecting the properties of the liquid crystal sealing agent. Examples of the organic filler (h) include silicone rubber fine particles, acrylic rubber fine particles, core shell type acrylic fine particles, and the like. These organic fillers may be used alone or in combination of two or more.

The average particle diameter of the organic filler which can be added is usually not more than 5 mu m, preferably not more than 2 mu m. When the average particle diameter is too large, it is difficult to form a cell gap. However, in the case of the silicone rubber powder as the organic filler, since the cell gap can be formed even when the average particle diameter is large, the preferable average particle diameter of the silicone rubber powder is 15 占 퐉 or less.

When the liquid crystal sealing agent of the present invention contains the organic filler, the content thereof is preferably 40 mass% or less, more preferably 30 mass% or less, based on the total amount of the liquid crystal sealing agent. The lower limit may be 0 mass%. But it is usually preferably 1% by mass or more, and more preferably 5% by mass or more. If it is excessively large, viscosity becomes high and formation of a cell gap becomes difficult. The form containing the organic filler in the liquid crystal sealing agent of the present invention is one of the preferred forms.

It is also a preferred embodiment of the present invention that a silicone rubber fine particle and an organic filler such as a (meth) acrylic resin fine particle, preferably a core shell type (meth) acrylic fine particle are used in combination as an organic filler. In that case, it is preferable to use the silicone rubber fine particles in a proportion of usually 1 to 10 parts by mass, preferably 3 to 7 parts by mass, relative to 1 part by mass of the other organic filler.

In the liquid crystal sealing agent of the present invention, additives such as a photo radical polymerization initiator, an organic solvent, a pigment, a leveling agent, and an antifoaming agent may be added, if necessary.

Next, some of the preferable forms of the sealing agent of the present invention will be described.

1. In the invention described in any one of (5) to (14) described in the "means for solving the problems", the curable resin (b) is in the form of a combination of an epoxy resin and a (meth) .

2. The epoxy resin composition according to 1 above, wherein the content of the epoxy resin is 3 to 40 mass% and the content of the (meth) acrylated epoxy resin is 60 to 97 mass% with respect to the total amount of the curable resin (b).

3. In the case where the curing accelerator (e) is included in the above 1 or 2 (the invention described in (11) to (14) of (5) to (14) Is in the range of 0.5 to 15 mass%, preferably 1 to 8 mass%, based on the total amount of the sealing agent of the present invention.

4. In the above item 3, the curing accelerator (e) is an isocyanatomene skeleton-containing polyhydric carboxylic acid curing accelerator.

5. In the above-mentioned 4, the curing accelerator (e) is tris (carboxy C1-C3 alkyl) isocyanurate.

(6) The positive electrode active material according to any one of (1) to (5) above, which contains the coupling agent (f) , The content of the coupling agent (f) is 0.05 to 3% by mass relative to the total amount of the sealing agent of the present invention.

7. The method according to item 6, wherein the coupling agent (f) is a silane coupling agent.

8. The form according to any one of 1 to 7, wherein the polythiol compound (g) is contained in an amount of 0.1 to 10% by mass based on the total amount of the sealing agent of the present invention.

9. The foam according to any one of 1 to 8, wherein the organic filler (h) is contained in an amount of 1 to 40% by mass based on the total amount of the sealing agent of the present invention.

In order to obtain the liquid crystal sealing agent of the present invention, the above epoxy resin and / or (meth) acrylated epoxy resin (b) and, if necessary, a coupling agent and additives are dissolved and mixed, The heat radical generating agent (a), the inorganic filler (d), the curing accelerator (e) and other optional components are suitably added and mixed with a conventional mixing apparatus such as three rolls, The mixture can be uniformly mixed by a mill, a ball mill, or the like. After mixing, it is preferable to carry out filtration treatment to remove foreign matter.

In the liquid crystal display cell of the present invention, a pair of substrates on which predetermined electrodes are formed are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealing agent of the present invention, and liquid crystal is sealed in the gap. The type of liquid crystal enclosed is not particularly limited.

Here, the substrate is made of glass, quartz, plastic, silicon, or the like. In the method for producing a liquid crystal display cell in the thermosetting liquid crystal dropping method, first, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention and mixed. Examples of the spacer include glass fibers, silica beads, polymer beads, and the like. The amount thereof is usually from 0.1 to 4 parts by mass, preferably from 0.5 to 2 parts by mass, more preferably from 0.5 to 2 parts by mass, per 100 parts by mass of the liquid crystal sealing agent, More preferably about 0.9 to 1.5 parts by mass.

A liquid sealing agent containing a spacer is applied to one side of the substrate by a dispenser or the like to form a bank (dummy sealing), and then the liquid sealing substrate is further coated with a sealing agent for one week at the outermost periphery (Pile sealing). After that, liquid crystal is dropped inside the bank of the inner sealing, and the other glass substrate is covered with each other in vacuum, and then the gap formation is performed by opening to the atmospheric pressure. Since the dummy sealing agent for keeping the liquid crystal sealing substrate in vacuum is not in contact with the liquid crystal and is removed after the completion of the liquid crystal cell, the same liquid sealing agent as that of the liquid crystal sealing agent can also be used as another UV curable sealing agent, visible light curable sealing agent, A thermosetting sealing agent can be used. When a UV curable sealing agent or a visible light curable sealing agent, which is a photo-curable sealing agent, is used for dummy sealing after forming a vacuum gap, the dummy sealing portion is cured by irradiating ultraviolet rays or visible light to the dummy sealing portion by an ultraviolet ray irradiator or a visible light irradiating device. When the photo-curable sealant is not used for dummy sealing, the light irradiation step is omitted. The liquid crystal display cell of the present invention can be obtained by heating the gap-formed substrate at 90 to 130 DEG C for 1 to 2 hours, and then removing the dummy sealing portion.

The liquid crystal display cell of the present invention thus obtained is free of display defects due to liquid crystal contamination, and is excellent in adhesiveness and humidity resistance reliability.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is not limited at all by the following examples.

Unless otherwise stated in the examples, "parts" means "parts by mass" and "%" means% by mass.

Example A

[Synthesis of 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane] (Silylated benzopinacol)

100 parts (0.28 mol) of a commercially available benzopinacol (TOKYO CHEMICAL INDUSTRY CO., LTD.) Were dissolved in 350 parts of dimethyl formaldehyde. To this was added 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (Shin-Etsu Chemical Co., Ltd.) as a silylating agent, and the mixture was heated to 70 占 폚 and stirred for 2 hours. The resulting reaction solution was cooled, and 200 parts of water was added while stirring to precipitate the product and inactivate the unreacted silylating agent. The precipitated product was separated by filtration and sufficiently washed with water. Then, the obtained product was dissolved in acetone, recrystallized by adding water, and purified. 105.6 parts (yield: 88.3%) of the desired 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane was obtained.

Analysis by HPLC (high performance liquid chromatography) showed that the purity was 99.0% (area percent).

And a molecular ion peak of 438 was obtained by HPLC-MASS (high performance liquid chromatography mass spectrometry). Further, a hydroxyl group proton 5.8 ppm (1H), siloxymethyl proton 0.0 ppm (9H), phenyl protons 7.1 ppm (16H) and 7.4 ppm (4H) were obtained as chemical shift values from the NMR spectrum (solvent DMSO-d6) It was identified as a target. The NMR spectrum thereof is shown in Fig.

Further, it is considered that the benzopinacol derivative has a higher steric hindrance when one of the two tertiary alcohols reacts, and the reactivity of the other hydroxyl group is further lowered, so that the silyl group is selectively introduced to one side in the above reaction.

Experimental Example One

For the purpose of examining the effect of the thermal radical generator of the present invention, the gelation time (time for curing on a hot plate at 120 캜) and the foaming test at 120 캜 of the sample were carried out.

(Test Methods)

10 parts of acrylic acid adduct of bisphenol A type epoxy resin (NIPPON KAYAKU Co., Ltd. .: R93100), 1 part of 1-hydroxy-2-trimethylsiloxane of the present invention as a thermal radical generator in Test Example 1 Tetra-phenylethane, benzopinacol in Test Example 2 (for comparison) and t-butylperoxy-2-ethylhexanoate (KAYAKU AKUZO CO ., TLD .: Kayaester O) were mixed in a three-roll mill, and the respective samples were adjusted.

The obtained sample was placed on a hot plate at 120 占 폚 and visually observed for curing time (gelation time at 120 占 폚) and turbidity due to foaming of the cured product. The results are shown in Table 1. The curing time was measured by bringing the glass rod into contact with the sample and measuring the time until the sample was not pulled out of the thread.

The evaluation criteria for the presence or absence of turbidity due to foaming are as follows.

Evaluation of turbidity caused by foaming

?: The cured product is transparent without clouding due to foaming.

?: The cured product was slightly cloudy due to foaming, and the transparency was slightly lowered.

X: White turbidity due to foaming was clearly recognized throughout the cured product, and transparency was clearly lowered.

As shown in Table 1, the thermal radical generating agent of the present invention (Test Example 1) is applicable to various uses requiring transparency since the curing rate is fast, there is no foaming, and no turbidity occurs.

On the other hand, in Test Example 2 as a comparative object, there is no problem in transparency, but there is a problem in workability because of a long curing time, and Test Example 3 is superior in terms of curing time, but turbidity due to foaming occurs, It is not suitable for applications requiring transparency, and there is concern about deterioration of the physical properties of the cured product due to foaming.

Example 1, 2, Comparative Example 1, 2

The resin solution was obtained by mixing the acrylated epoxy resin, the epoxy resin and the silane coupling agent described in Table 1 below.

The inorganic filler, the thermosetting agent, the curing accelerator, the silylated benzopinacol, the polythiol compound, the silicone rubber powder (organic filler) and the core shell acrylic fine particles (organic filler) were compounded in the amounts shown in Table 1 , And kneaded by three rolls to obtain the liquid crystal sealing agents of Examples 1 and 2.

A liquid crystal sealing agent of Comparative Example 1 was obtained in the same manner as in Example 1 except that benzopinacol was used in the composition of Example 1 in place of benzylpinacol in place of silylated benzopinacol.

A liquid crystal sealing agent of Comparative Example 2 was obtained in the same manner as in Example 1 except that organic peroxides were used in the composition of Example 1 in place of the silylated benzopinacol in the amounts shown in Table 2 .

Reference Synthetic example One [ Of resorcine diglycidyl ether Synthesis of whole acrylate]

140 parts of resorcine diglycidyl ether resin were dissolved in 160 parts of toluene. To this was added 0.48 part of dibutylhydroxytoluene as a polymerization inhibitor, and the temperature was raised to 60 占 폚. Thereafter, 100 parts of acrylic acid (equivalent to 100% of the epoxy group of the resorcine diglycidyl ether resin) was added and the temperature was further raised to 80 DEG C, 0.96 part of trimethylammonium chloride as a reaction catalyst was added thereto, Lt; / RTI > The obtained reaction solution was washed with water and toluene was distilled off to obtain 241 parts of epoxy acrylate of resorcinol.

The values in Table 2 are parts by weight.

* 1: The total acrylate of the resorcine diglycidyl ether (the compound obtained in Reference Synthesis Example 1)

* 2: Resorcine diglycidyl ether (NIPPON KAYAKU Co., Ltd., trade name: RGE-HH)

* 3: spherical silica (Shin-Etsu Chemical Co., Ltd., trade name: X-24-9163A; primary average particle size: 110 nm)

* 4: Silicone rubber powder (Shin-Etsu Chemical Co., Ltd., trade name: KMP-598;

* 5: 3-glycidoxypropyltrimethoxysilane (CHISSO CORPORATION, trade name: Sila-ace ^RTM S-510)

* 6: N-2 (aminoethyl) 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name: KBM603)

* 7: Tris (2-hydrazinocarbonylethyl) isocyanurate finely pulverized product (trade name: JAPAN FINECHEM COMPANY, INC., Trade name: HCIC, finely ground with a jet mill at an average particle size of 1.5 μm)

* 8: 1-Hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane (Compound obtained in the same manner as in Example A (silylated benzopinacol) was jet milled to an average particle diameter of 1.9 mu m Finely pulverized)

* 9: Benzopinacol micronized product (obtained by finely milling benzopinacol from Tokyo Chemical Industry Co., Ltd. with a jet mill to an average particle size of 1.9 mu m)

* 10: t-Butyl peroxy-2-ethylhexanoate ((KAYAKU AKUZO CO., TLD., Trade name: Kayaester ^RTM O)

* 11: Pentaerythritol tetrakis (3-mercaptobutyrate) (SHOWA DENKO KK, trade name: Karenz ^RTM MT PE1)

* 12: Tris (3-carboxypropyl) isocyanurate pulverized product (product of SHIKOKU CHEMICALS CORPORATION, trade name: C3-CIC acid was finely pulverized with a jet mill to an average particle size of 1.5 탆)

* 13: core shell acrylic fine particles (GANZ CHEMICAL CO., LTD., Trade name: F351S; average particle diameter 0.3 탆)

Preparation of liquid crystal cell for evaluation

1 g of a glass fiber having a thickness of 5 탆 was added as a spacer to 100 g of each of the liquid crystal sealing agents of Examples 1 and 2 or Comparative Examples 1 and 2, mixed and defoamed, and filled in a syringe. An alignment film solution (trade name: PIA-5540-05A, CHISSO CORPORATION) was applied to a glass substrate provided with an ITO transparent electrode, followed by baking and rubbing treatment. A sealing pattern and a dummy sealing pattern were applied to each of the liquid crystal sealing agents in the examples and comparative examples packed in a syringe on this substrate using a dispenser (SHOTMASTER 300, manufactured by Musashi Engineering Inc.), and then a liquid crystal (trade name: JC- 5015LA, CHISSO CORPORATION) was dropped in the range of the sealing pattern. In addition, an in-plane spacer (trade name: Natoco spacer KSEB-525F, Natoco Co., ltd., Gap width after bonding: 5 μm) was sprayed on the glass substrate which had been subjected to one rubbing treatment and was hot- And adhered to the substrate on which the previous liquid drop was completed. Thereafter, a gap was formed in the atmosphere to form a gap, and the mixture was placed in an oven at 120 ° C and cured by heating for 1 hour to prepare a liquid crystal test cell for evaluation.

Table 2 shows the results of observing the sealing shape and the liquid crystal alignment dizziness of the prepared liquid crystal cell for evaluation by a polarizing microscope. The gaps of the prepared liquid crystal cells were measured using a liquid crystal property evaluation apparatus (trade name: OMS-NK3, CHUO PRECISION INDUSTRIAL CO., LTD.). The sealing shape, the liquid crystal alignment disturbance and the gap of the liquid crystal cell were evaluated in the following four steps.

Evaluation of sealing shape

○: There is no disturbance in the linearity of sealing.

DELTA: Deformation of the sealing is recognized, but it is a level at which the sealing of the liquid crystal is not problematic.

X: A level at which a liquid crystal is plugged into the sealing and a problem may occur in sealing the liquid crystal.

XX: The sealing is broken and the cell can not be formed.

Evaluation of Liquid Crystal Cell Gap

?: The cell gap was uniformly 5 占 퐉.

DELTA: There is a cell gap of about 5.5 mu m in the cell.

X: There is a cell gap of 6 mu m or more in the cell.

XX: The sealing is broken and the cell can not be formed.

Evaluation of Liquid Crystal Orientation

?: No alignment disturbance of the liquid crystal in the vicinity of the sealing.

?: There is alignment disturbance in a slight region in the vicinity of the sealing.

X: There is orientation disturbance from the vicinity of the sealing to the wide area.

XX: The sealing is broken and the cell can not be formed.

Liquid Crystal Sealing Adhesive Strength Test

1 g of a glass fiber having a thickness of 5 탆 was added as a spacer to 100 g of the liquid sealing agent of Examples 1 and 2 or Comparative Examples 1 and 2, followed by mixing and stirring. This liquid crystal sealing agent was applied on a glass substrate of 50 mm x 50 mm, and a glass piece of 1.5 mm x 1.5 mm was laminated on the liquid crystal sealing agent and placed in an oven at 120 deg. C for 1 hour to cure. The shear bond strength of the glass piece was measured using a bond tester (trade name: SS-30WD, SEISHIN TRADING CO. LTD.). The results are shown in Table 3 below.

Liquid crystal sealing agent anti-moisture adhesive strength test

The measurement sample was subjected to a pressure cooker test machine (trade name: TPC-411, manufactured by Davis ESPEX Co., Ltd.) under the conditions of 121 캜, 2 atm, and a humidity of 100% The sample charged for 20 hours was measured using a bond tester (trade name: SS-30WD: SEISHIN TRADING CO, LTD.). The results are shown in Table 4 below.

Portlife

Using a R-type viscometer (Toki Sangyo co., Ltd.), the viscosity change of the obtained liquid crystal sealing agent at 25 캜 was measured. Table 4 shows the viscosity increase rate (%) with respect to the initial viscosity.

As shown in Tables 3 and 4, the liquid crystal sealing agent of the embodiment of the present invention using silylated benzopinacol as a radical generating agent is superior in liquid crystal alignment as compared with the liquid crystal sealing agent of Comparative Example 1 in which benzopinacol is used as a radical generating agent. But also remarkably excellent in points, adhesive strength, and adhesion strength after humidity resistance.

(Industrial availability)

From the above, the tetraphenyl ethane derivative of the present invention is useful as a thermal radical generating agent having a short gel time and no foaming in the radical curable resin composition, since the radical-generating ability of heat is high and there is no foaming. In addition, since there is no decrease in transparency due to foaming or lowering of physical properties of other cured products, a resin cured product having high transparency and good physical properties can be obtained. When the tetraphenyl ethane derivative is used as a heat radical generating agent in a liquid crystal sealing agent, the sealing agent has low contamination of the liquid crystal, has a long pot life, and can form a sealing film and a cell gap. Therefore, Workability is also good, and further, the adhesive strength after bonding and the adhesion strength after humidity resistance are excellent. Therefore, it is particularly suitable as a thermosetting liquid crystal sealing agent for a liquid crystal dropping method.

Claims

A tetraphenyl ethane derivative of the formula (1 '):

In this formula,
One of Y ^{1 '} and Y ^2' is a hydrogen atom and the other is a silicon atom,
R ¹ to R ⁶ each independently represent a hydrogen atom or a straight or branched alkyl group having 1 to 4 carbon atoms,
X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group,
only,
Y ¹ R ¹ ~R ³ or R ⁴ ~R ^6, which respectively coupled to the ^'or Y ^2' is Y ^{1 'or} Y ^2' is a hydrogen atom do not exist.

2. The compound according to claim 1, wherein in the formula (1 '), when any one of Y ^1' and Y ^{2 '} is a hydrogen atom and the other is a silicon atom, R ¹ R ² R ³ Y ^{1 '-,} or ^{R 4 R 5 R 6 Y 2} ' - di is a silyl group (having 1 to 4 carbon atoms in the straight-chain or branched alkyl) silyl group, or a tri (straight chain or branched alkyl of 1 to 4 carbon atoms), X ¹ ~X ⁴ < / RTI > are hydrogen atoms.

The compound according to claim 1, wherein in the formula (1 '), one of Y ^1' and Y ^{2 '} is a hydrogen atom and the other is a silicon atom, and when it is a silicon atom, R ¹ R ² R ³ Y ^{1 '} - or R ⁴ R ⁵ R ⁶ Y ^2' - is trimethylsilyl, triethylsilyl or t-butyldimethylsilyl, and all of X ^{1 to} X ⁴ are hydrogen atoms.

2. The tetraphenyl ethane derivative according to claim 1, which is 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane of the formula (2).

(a) a tetraphenyl ethane derivative of the following formula (1), (b) either or both of an epoxy resin or a (meth) acrylic acid adduct of an epoxy resin, (c) a thermosetting agent, and Thermosetting liquid crystal sealing agent for liquid crystal dropping method characterized by:

In this formula,
Y ¹ or Y ² each independently represents a hydrogen atom, a phenyl group, or a silicon atom,
R ¹ to R ⁶ each independently represent a hydrogen atom or a straight or branched alkyl group having 1 to 4 carbon atoms,
X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom,
only,
Y ¹ or R ¹ ~R ³ or R ⁴ ~R ^6, which respectively coupled to the Y ² when Y ¹ or Y ² is a hydrogen atom is not present,
And the case where all of Y ¹ and Y ² are hydrogen atoms is excluded.

The liquid crystal sealing agent according to claim 5, wherein (a) the tetraphenyl ethane derivative of the formula (1) is a tetraphenyl ethane derivative according to any one of claims 1 to 4.

The liquid crystal sealing agent according to claim 5, wherein (a) the tetraphenyl ethane derivative of the formula (1) is a solid powder having an average particle size of 5 탆 or less.

The liquid crystal sealing agent according to claim 5, wherein the curing agent (c) is a latent curing agent having a melting point or softening point of 100 ° C or higher.

6. The liquid crystal sealing agent according to claim 5, wherein (d) the inorganic filler is alumina and / or silica.

The liquid crystal sealing agent according to claim 5, wherein the inorganic filler (d) has an average particle diameter of 10 to 2000 nm.

The liquid crystal sealing agent according to claim 5, which comprises (e) a curing accelerator.

The liquid crystal sealing agent according to claim 5, which further comprises (f) a coupling agent.

(B) a (meth) acrylic acid adduct of an epoxy resin and / or an epoxy resin is added in an amount of 0.1 to 10 mass% based on the total amount of the liquid crystal sealing agent. (C) 5 to 60 parts by mass of the thermosetting agent relative to 100 parts by mass of the component (b), and (d) 1 to 5 parts by mass of the inorganic filler relative to the total amount of the liquid crystal sealing agent. To 30% by mass of the liquid crystal sealing agent.

(A) when any one of Y ¹ and Y ^{2 in} the formula (1) is a hydrogen atom and the other is a silicon atom and is a silicon atom, R ¹ R ² R ³ Y ¹ - or R ⁴ R ⁵ R ⁶ Y ² - is a ^divalent (straight chain or branched alkyl) silyl group having 1 to 4 carbon atoms or a tri (straight or branched chain) alkylsilyl group having 1 to 4 carbon atoms, and X ^{1 to} X ⁴ (B) a (meth) acrylic acid adduct of an epoxy resin or an epoxy resin, (c) a latent curing agent having a melting point or softening point of 100 ° C or higher as a heat curing agent, (d) An inorganic filler, and (e) a curing accelerator, or (f) a coupling agent.

A liquid crystal display cell sealed with a cured product of the liquid crystal sealing agent according to claim 5.

A radical generator comprising the tetraphenyl ethane derivative according to claim 1 as an active ingredient.

A method for producing a thermosetting liquid crystal sealing agent, wherein a tetraphenyl ethane derivative of the formula (1) described in claim 5 is used as a radical generating agent.

A cured product obtained by thermally curing a radical curable resin composition comprising the tetraphenyl ethane derivative according to claim 1.

A process for producing a tetraphenyl ethane derivative of the following formula (1 ') for reacting a benzopyran of formula (3) with a silylating agent:

In this formula,
X ^{1 to} X ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen group,
One of Y ^{1 '} and Y ^2' is a hydrogen atom and the other is a silicon atom,
R ¹ to R ⁶ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
Stage, Y ¹ R ¹ ~R ³ or R ⁴ ~R ^6, which respectively coupled to the ^'or Y ^2' is Y ^{1 'or} Y ^2' is not present in the case of a hydrogen atom.

According to claim 1, 'in, Y ^1, formula ^(1)' or Y ^{2 'is} the one case a hydrogen atom, the other is a silicon atom, a silicon atom, R ¹ ~R ^3, or R ⁴ ~ R ⁶ is, independently of each other, a straight-chain or branched alkyl group having 1 to 4 carbon atoms.