TWI511974B - Novel tetraphenyl ethane derivative, radical generating agent containing the same, cured article of the same and method for producing same - Google Patents

Description

Novel tetraphenylethane derivative, radical generator containing the same, hardened product of the derivative, and method for producing the same

The present invention relates to a novel silyl tetraphenyl-1,2-ethanediol (silylbenzopinacol), its use as a thermal radical generating agent, a liquid crystal sealing agent containing the same, and a liquid crystal using the same Display unit.

In the past, azo compounds, organic peroxides, benzoin, and benzoin ethers have been widely used as radical generators which are hardened by radical polymerization of a radical polymerizable compound. , acetophenones, tetraphenyl-1,2-ethanediols, and the like.

An azo compound or an organic peroxide which is most likely to generate a radical by thermal cracking is used as a radical generating agent in products such as an adhesive, a sealant, a gap formation agent, and a molding material. However, since the above-mentioned radical generating agent is generated by a gas such as nitrogen or carbon dioxide at the time of radical generation, there is a concern that such a gas greatly impairs the characteristics of the above-mentioned product. For example, there are characteristics of damaged doubts, such as The strength is lowered, the heat resistance is lowered, and the shape of the molded product is not good. Examples of the other radical generating agent include benzoin, benzoin ether, acetophenone, and tetraphenyl-1,2-ethanediol. In these cases, although foaming during heating is small, there is a problem that the radical generating ability is poor and the desired performance (reactivity and hardenability) cannot be obtained.

Patent Document 1 discloses that in a system in which both ultraviolet rays and heat are used for curing, tetraphenyl-1,2-ethanediol as a thermal radical generating agent is used to harden unshaded shadow portions. Further, Patent Document 2 discloses that an inferrer-type radical generating agent is effective for the production of a contact lens, a lens of various lenses or a dental material, and examples thereof include tetraphenyl-1,2. - ethylene glycol. In the patent document 3, the thermal radical generating agent used for the sealing agent for flat panel displays is, for example, tetraphenyl-1,2-ethanediol.

Patent Documents 1 and 3 further exemplify a chemically modified compound of tetraphenyl-1,2-ethanediol. It is described that the compound exerts a desired effect. However, tetraphenyl-1,2-ethanediol is a tertiary alcohol and its hydroxyl group is affected by the steric hindrance of the phenyl group, so that the reactivity is not good, and it is still not suitable for obtaining a stable derivative. Report of the person.

Further, one of the fields of use of the thermal radical generating agent is, for example, a liquid crystal sealing agent for a liquid crystal display unit.

In recent years, as a method of manufacturing a liquid crystal display unit, a large-sized liquid crystal display unit has been introduced as a liquid crystal display unit manufacturing method in which a liquid crystal dropping method having a higher mass production performance than a liquid crystal display unit of a liquid crystal vacuum injection method has been introduced. Manufacturing (refer to Patent Document 4). Liquid crystal dropping method Applying a liquid crystal sealing agent to the bank (the main seal) on the liquid crystal substrate, applying a sealant to one of the outermost periphery (pseudo-sealing), dropping the liquid crystal inside the inner seal, and then laminating the opposite side in the vacuum The other liquid crystal substrate is sealed by releasing the liquid crystal to atmospheric pressure, and the sealing portion is cured by UV irradiation and heating to complete the method of manufacturing the liquid crystal display unit. The liquid crystal sealing material used for the liquid crystal sealing in this manufacturing method is not a conventional thermosetting liquid crystal sealing agent, and a liquid crystal sealing agent of a photothermal curing type is generally used. The reason why the conventional thermosetting liquid crystal sealing agent (also referred to as a thermosetting liquid crystal sealing agent) cannot be used in the liquid crystal dropping method is because the liquid crystal dropping method is performed by the conventional thermosetting liquid crystal sealing agent, Heating under reduced pressure causes the thermal expansion of the liquid crystal during heating and the viscosity caused by the heating of the liquid crystal sealing agent to decrease, and the seal is bursted, and the liquid crystal cannot be sealed.

When the liquid crystal sealing agent is applied to a liquid crystal substrate by a dispenser or the like to form a liquid crystal sealing agent, the liquid crystal is dropped on the inside of the bank, and the opposite substrate is bonded in a vacuum. The sealing portion is irradiated with light such as ultraviolet rays to be temporarily cured, and then the liquid crystal sealing agent is thermally cured at about 120 ° C for about 1 hour to produce a liquid crystal cell.

However, in the case of a photothermal curing type, it is necessary to irradiate the liquid crystal sealing agent with light such as ultraviolet rays. However, with the narrow frame of the liquid crystal cell in recent years, the following problems occur.

That is, since the liquid crystal sealing portion is shielded by wiring or a black matrix, a portion where the liquid crystal sealing agent is not irradiated with light is generated, and an unhardened portion is generated. There is a possibility that the unhardened portion is exposed to liquid crystal infiltration or liquid crystal contamination during the heat hardening step. Therefore, when designing a liquid crystal cell, it is generated It must be designed so that the sealant illuminates as much light as possible. Further, since the liquid crystal or the alignment film is degraded by the ultraviolet irradiation, it is necessary to shield the liquid crystal portion with a light-shielding mask in the ultraviolet irradiation step in order to prevent the ultraviolet rays from being irradiated to the liquid crystal. Further, as the size of the liquid crystal glass substrate increases, the size of the ultraviolet irradiation device increases, and problems such as an increase in the operating cost of the ultraviolet irradiation device may occur.

In view of the above, in recent years, it has been desired to realize a thermosetting liquid crystal sealing agent which can be used as a liquid crystal display unit in a liquid crystal dropping method, which is not required to be irradiated with ultraviolet rays, and which can be made into a liquid crystal display unit by heat hardening (a thermosetting liquid crystal for liquid crystal dropping method) Sealants).

Up to now, proposals for a thermosetting liquid crystal sealing agent for a liquid crystal dropping method have been underway. For example, Patent Document 5 proposes a heat hardening of 3 to 40 parts by weight based on 100 parts by weight of a curable resin having a molecular weight of 3.5 × 10 ^-4 or more with respect to the number of hydrogen-bonding functional groups in one molecule. The liquid crystal dropping method of the agent uses a heat-hardening liquid crystal sealing agent. It is also revealed that low liquid crystal contamination is achieved by using such a liquid crystal sealing agent. However, with the liquid crystal dropping method using the thermosetting liquid crystal sealing agent, it is difficult to sufficiently solve the following major problems: the above-mentioned low viscosity due to heating, and the dam of the liquid crystal sealing agent is broken during the hardening process, causing liquid crystal leakage. Problem (the problem of seal burst); and the composition of the liquid crystal sealant which is low in viscosity due to heating, and is also easier to be heated than usual due to heating to the NI point (the temperature from the isotropic phase to the liquid crystal phase) Dissolved in the flowing liquid crystal to cause liquid crystal contamination.

Further, in Patent Document 6, liquid crystal density by adding a gelling agent The sealing agent is resistant to seal bursting and can maintain a sealed shape in a liquid crystal dropping method which is only thermally hardened. However, the contamination of the liquid crystal by the liquid crystal sealing agent at the time of heat hardening which is a problem of the thermosetting liquid crystal dropping method is not solved.

Patent Document 7 proposes a method of pre-baking after applying a liquid crystal sealing agent composed of a thermosetting resin, followed by liquid crystal dropping and vacuum bonding. However, the resin composition of the specific liquid crystal sealing agent is not clearly disclosed.

Patent Documents 8 and 9 propose a liquid crystal sealing agent for a liquid crystal dropping method which is a pre-baking step of a B-stage (semi-hardening) treatment. Since this method requires a B-stage treatment at 80 ° C for 20 minutes, it has the disadvantage of a long step time. Further, in order to shorten the B-stage treatment time of 20 minutes, for example, when the treatment temperature is raised to 100 ° C or higher, the liquid crystal sealing agent described is hard to react and is therefore inferior.

Patent Document 7 proposes a liquid crystal sealing agent comprising a pyrolysis type radical generating agent, a compound containing an unsaturated double bond, and a polyaddition type thermal curing agent. Here, the production of a liquid crystal display element in which a part of UV irradiation is performed by atmospheric pressure bonding via a liquid crystal substrate is described. However, it is not described that vacuum pressure bonding is performed via a liquid crystal substrate, and liquid crystal display elements are produced only by thermal curing without UV irradiation.

As described above, there is no heat-curing type liquid crystal dropping sealing agent which solves all the problems of the thermosetting sealing agent in the liquid crystal dropping method, and the liquid crystal dropping method which only heat-hardensing has not been realized.

In addition, in recent years, the expectation of expanding the display area more than the size of the substrate has become stronger. Therefore, the design of a liquid crystal cell such as a narrow frame or a liquid crystal sealing width which narrows the peripheral portion of the liquid crystal sealing is gradually developed. As a result, a liquid crystal sealing agent which can form a narrow sealing width and a uniform sealing shape and which is not easily dissipated is gradually sought, and further, a liquid crystal sealing agent which is strong in strength even if the sealing width is fine is gradually sought. Further, a liquid crystal sealing agent having a small change in coating conditions of a liquid crystal sealing agent during a working time and having a long pot life is sought.

In addition, in recent years, with the popularization of liquid crystal televisions and the like, the high-speed reactivity of liquid crystals has been improved for the playback of films, and thus the cell gap of the liquid crystal (the gap between the two substrates filled with liquid crystal) is gradually narrowed. It is gradually sought to obtain a liquid crystal sealing agent having a narrow cell gap easily when a liquid crystal substrate is vacuum-bonded.

Then, with regard to the demand for a longer life of the liquid crystal cell, deterioration of the high-humidity condition of the liquid crystal sealing becomes a problem. Therefore, a liquid crystal sealing agent having a small deterioration in the adhesion strength of the liquid crystal sealing after the high-temperature and high-humidity test is gradually sought.

As described above, the liquid crystal dropping method capable of realizing the thermosetting type is sought, the vacuum bonding of the substrate, the sealing without bursting by heating, and the absence of liquid crystal contamination, followed by the strength after the strength and moisture resistance test, and the sealing coating A thermosetting liquid crystal sealing agent for a liquid crystal dropping method which has a good cloth property and a long service life at room temperature and which easily achieves a narrow cell gap.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 57-53508

[Patent Document 2] Japanese Patent Laid-Open No. 11-21304

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-10870

[Patent Document 4] Japanese Special Fair 8-20627

[Patent Document 5] Japanese Patent No. 3955038

[Patent Document 6] Japanese Patent No. 3976749

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2005-92043

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2007-199710

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2007-224117

The present invention is based on the aforementioned prior art, and the first object of the present invention is to develop a novel thermal radical generating agent which does not foam and has higher activity when heated.

Further, a second object of the present invention is to provide a thermosetting liquid crystal sealing agent for a liquid crystal dropping method which is not required to be irradiated with ultraviolet rays. In addition, it provides a liquid crystal dropping method thermosetting type which has low liquid crystal contamination, strong adhesion strength after adhesion strength and moisture resistance test, good sealing linearity, long service life at room temperature, and easy narrow cell gap filling. Liquid crystal sealing agent (hereinafter also referred to as thermosetting liquid crystal sealing agent for liquid crystal dropping method).

In order to solve the above problems, the inventors of the present invention have found that at least one hydroxyl group of tetraphenyl-1,2-ethanediol which may have a substituent on the benzene ring is decanolated, so that it is not heated when heated. A novel thermal radical generating agent having a higher activity and a higher activity, and a thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the above object can be obtained by using the thermal radical generating agent. The present invention has been completed.

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

(1) a tetraphenylethane derivative represented by the following formula (1'), (wherein, Y ^{1 '} or Y ^{2 '} are each independently and represent a hydrogen atom or a halogen atom, and R ¹ to R ⁶ are each independently, and represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, X ¹ to X. ⁴ each independently, representing a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom; however, R ¹ to R ³ or R ⁴ respectively bonded to Y ^{1 '} or Y ^{2 '} To R ⁶ , when Y ^{1 '} or Y ^{2 '} is a hydrogen atom, it does not exist, and it is excluded that both Y ^{1 '} and Y ^{2 '} are hydrogen atoms, and further, Y ^{1 '} and Y ^{2 '} are excluded as a halogen atom. And all of R ¹ to R ⁶ are a methyl group, and all of X ¹ to X ⁴ are hydrogen atoms).

(2) The tetraphenylethane derivative according to the above (1), wherein one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other represents a halogen atom, When it is a halogen atom, R ¹ R ² R ³ Y ^1' - or R ⁴ R ⁵ R ⁶ Y ^2' - is two (straight or branched alkyl having 1 to 4 carbon atoms) decyl or tri (carbon number 1) To a straight or branched alkyl group of 4) fluorenyl, and X ¹ to X ⁴ are all hydrogen atoms.

(3) The tetraphenylethane derivative according to the above (1) or (2), wherein any one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other In the case of a deuterium atom, which is a deuterium atom, R ¹ R ² R ³ Y ^1' - or R ⁴ R ⁵ R ⁶ Y ^2' - is trimethyldecyl, triethyldecyl or tert-butyl Based on an alkyl group, and X ¹ to X ⁴ are all hydrogen atoms.

(4) The tetraphenylethane derivative according to any one of the above (1) to (3) which is 1-hydroxy-2-trimethyldecyloxy group represented by the following formula (2) - 1,1,2,2-tetraphenylethane

(5) A thermosetting liquid crystal sealing agent for a liquid crystal dropping method, comprising: (a) a tetraphenylethane derivative represented by the following formula (1); (b) an epoxy resin or an epoxy resin Any one or both of the (meth)acrylic acid adducts of the resin; (c) a thermal hardener; and (d) an inorganic filler, Wherein Y ¹ or Y ² are each independently and represent a hydrogen atom, a phenyl group or a fluorene atom, and R ¹ to R ⁶ are each independently, and represent a hydrogen atom or a straight or branched alkyl group having 1 to 4 carbon atoms, X ¹ to X ⁴ each independently represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom; however, R ¹ to R ³ or R ⁴ respectively bonded to Y ¹ or Y ^{2 are} R ⁶ , when Y ¹ or Y ² is a hydrogen atom, is absent, and excludes the case where both Y ¹ and Y ² are hydrogen atoms).

(6) The liquid crystal sealing agent according to the above (5), wherein (a) the tetraphenylethane derivative of the formula (1) is any one of the above (1) to (4) or (20) below. The tetraphenylethane derivative described in the above.

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

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

The liquid crystal sealing agent according to any one of the above-mentioned (5), wherein (d) the inorganic filler is alumina and/or cerium oxide.

(10) The liquid crystal sealing agent according to any one of the above (5), 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) above, wherein Contains (e) a hardening accelerator.

The liquid crystal sealing agent of any one of (5) to (11) containing (f) coupling agent.

The liquid crystal sealing agent according to any one of the above-mentioned (5), which contains (a) tetraphenylethane derivative of the formula (1) with respect to the total amount of the liquid crystal sealing agent. a range of from 0.1 to 10% by mass of the substance, (b) a range of from 30 to 75% by mass of the (meth)acrylic acid addition product of the epoxy resin and/or the epoxy resin; and 100 parts by mass of the component (b), c) a range of 5 to 60 parts by mass of the heat hardener; and a range of 1 to 30% by mass of the (d) inorganic filler with respect to the total amount of the liquid crystal sealing agent.

(14) The liquid crystal sealing agent according to any one of the above (5) to (13), wherein: (a) in the formula (1), any one of Y ¹ or Y ² is a hydrogen atom , the other represents a ruthenium atom, and when it is a ruthenium atom, R ¹ R ² R ³ Y ¹ - or R ⁴ R ⁵ R ⁶ Y ² - is two (straight or branched alkyl group having 1 to 4 carbon atoms) decane a tetraphenylethane derivative having a hydrogen atom or a triple or a branched or branched alkyl group having ¹ to ⁴ carbon atoms; and (b) an epoxy resin or an epoxy resin; Either or both of (meth)acrylic acid adducts; (c) a latent hardener having a melting point or softening point of 100 ° C or more as a thermal hardener; (d) an inorganic filler; and (e) hardening Either or both of the accelerator or (f) coupling agent.

(15) A liquid crystal display unit according to any one of (5) to (14) above The cured liquid crystal sealant is sealed.

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

(17) The use of the tetraphenylethane derivative of the formula (1) according to the above (5), which is used as the radical generator of the above (16) for producing a thermosetting liquid crystal sealing agent By.

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

(19) A process for producing a tetraphenylethane derivative represented by the following formula (1'), which is a tetraphenyl-1,2-ethanediol represented by the following formula (3) a reaction of a decylating agent, (wherein, Y ^{1 '} or Y ^{2 '} are each independently and represent a hydrogen atom or a halogen atom, and R ¹ to R ⁶ are each independently, and represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, X ¹ to X. ⁴ each independently, representing a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom; however, R ¹ to R ³ or R ⁴ respectively bonded to Y ^{1 '} or Y ^{2 '} To R ⁶ , when Y ^{1 '} or Y ^{2 '} is a hydrogen atom, it does not exist, and it is excluded that both Y ^{1 '} and Y ^{2 '} are hydrogen atoms)

(wherein, X ¹ to X ⁴ are each independently and represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom).

(20) The tetraphenylethane derivative according to the above (1), wherein one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other represents a halogen atom, When it is a halogen atom, R ¹ to R ³ or R ⁴ to R ⁶ are each independently a straight or branched alkyl group having 1 to 4 carbon atoms.

The tetraphenylethane derivative (also referred to as tetraphenyl-1,2- benzopinacol derivative) represented by the formula (1) used in the present invention is used as a thermal radical generating agent. The agent does not foam when heated, and can increase the reaction rate. Therefore, the thermal radical generating agent which is not suspected of deterioration in physical properties due to foaming can be widely used in various applications, for example, in the production of an adhesive, a sealant, a gap forming agent, a molding material, etc., and can be obtained. A product excellent in physical properties (hardened properties, adhesion strength, shape stability, etc.). In particular, it is preferably used as a thermal radical generating agent for a thermosetting liquid crystal sealing agent used in a liquid crystal dropping method.

The thermosetting liquid crystal sealing agent used as the thermal radical generating agent of the tetraphenylethane derivative represented by the above formula (1) used in the present invention is most suitable as a non-essential ultraviolet ray for the liquid crystal sealing portion. Liquid crystal drip A thermosetting liquid crystal sealing agent for use in the process (hereinafter referred to as a liquid crystal sealing agent of the present invention). Since the liquid crystal sealing agent has excellent properties such as low liquid crystal contamination, strong adhesion strength after adhesion strength and moisture resistance test, good sealing linearity, and long service life at room temperature, a liquid crystal cell having a narrow cell gap can be easily produced. As a result, a liquid crystal display unit having high yield, high reliability, and high quality can be manufactured. Further, the liquid crystal display unit of the present invention sealed by the cured product of the liquid crystal sealing agent of the present invention has no display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance.

Further, the tetraphenylethane derivative represented by the above formula (1') is a novel compound synthesized by the present inventors.

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

Hereinafter, the present invention will be described in detail.

In the following description, for the sake of simplicity, the general formula (1) will be described, but in addition to the description not included in the scope of the general formula (1'), any of the descriptions may be substituted with the general formula (1) ( 1'), similarly, also applies to the general formula (1'). In addition, the descriptions attached to Y ¹ and Y ² may be replaced by Y ^{1 '} and Y ^{2 '} , respectively, and the same applies to the range not included in Y ^{1 '} and Y ^{2 '} .

In the general formula (1) of the present invention, Y ¹ and Y ² each independently represent a hydrogen atom, a phenyl group or a fluorene atom, and at least one of them is a group other than a hydrogen atom. It is preferred that one of them is a hydrogen atom and the other is a deuterium atom.

In the general formula (1) in the invention, a linear or branched alkyl group having a carbon number of 1 to 4 (hereinafter simply referred to as a C1 to C4 alkyl group) in R ¹ to R ⁶ may, for example, be a methyl group or an ethyl group. , n-propyl, isopropyl, tert-butyl, and the like. Further, examples of the halogen atom in X ¹ to X ⁴ include a fluorine atom, a chlorine atom, a bromine atom and the like.

When Y ¹ or Y ² of the general 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 phenyl or 1 to 3 C1 a C4 alkyl substituted phenyl group, or a di C1 to C4 alkyl decyl group or a tri C1 to C4 alkyl decyl group, preferably a C1 to C4 alkyl decyl group or a tri C1 to 4 alkyl decyl group. Preferably, a tri-C1 to C4 alkyl decyl group is more preferred.

R ¹ R ² R ³ Y ¹ -, R ⁴ R ⁵ R ⁶ Y ² - in a straight or branched alkyl group having two or three carbon numbers of 1 to 4, 2 or 3 carbon atoms The alkyl groups of 1 to 4 may be the same or different, and the decyl group may, for example, be a di-C1 to C4 alkyl decyl group such as dimethyl decyl, diethyl decyl or methyl ethyl decyl; or A tri-C1 to C4 alkyl decyl group such as an alkyl group, a triethyl decyl group, a dimethylethyl decyl group, or a tert-butyl dimethyl decyl group. Among these, a C1 to C4 alkyl decyl group is preferred, and a trimethyl decyl group is more preferred.

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, and it is preferred that all of X ¹ to X ⁴ are a hydrogen atom.

Among the tetraphenylethane derivatives represented by the formula (1), preferred examples of the compound include 1-hydroxy-2-di or tri(C1 to C4 alkyl)decyloxy-1,1,2. 2-tetraphenylethane or 1,2-bis{di or tri(C1 to C4 alkyl)decyloxy}-1,1,2,2-tetraphenylethane, 1-hydroxy-2 -di- or tri-(C1 to C4 alkyl)decyloxy-1,1,2,2-tetraphenylethane is preferred, more preferably 1-hydroxy-2-tris(C1 to C4 alkyl)decane Oxyl-1,1,2,2-tetraphenylethane.

Further, 2 or 3 alkyl groups on the di- or tri-(C1 to C4 alkyl) nonyloxy decyl group in the above tetraphenylethane may be the same or different. For example, the tri(C1 to C4 alkyl) decyloxy group may include a trimethyl decyloxy group, a triethyl decyloxy group or a tert-butyl dimethyl decyloxy group.

Preferred examples of the tetraphenylethane derivative include, for example, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2. - bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(t-butyldimethylmethylalkoxy)-1,1,2,2 -tetraphenylethane, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1 2,2-Tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1,1,2,2-tetraphenylethane. Preferred are, for example, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1,2 , 2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylammonyloxy-1,1,2,2-tetraphenylethane.

Among them, preferred in the present invention are 1-hydroxy-2-trimethylnonyloxy-1,1,2,2-tetraphenylethane and 1-hydroxy-2-triethyldecyloxy. -1,1,2,2-tetraphenylethane or 1-hydroxy-2-tert-butyldimethylammonyloxy-1,1,2,2-tetraphenylethane, by formula (2 More preferably, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane is shown.

The tetraphenylethane derivative represented by the formula (1) of the present invention is characterized in that tetraphenyl-1,2-ethanediol represented by the formula (3) is decanolated by various decylating agents. structure.

The tetraphenylethane derivative represented by the formula (1) of the present invention can be used in the pyridine via tetraphenyl-1,2-ethanediol represented by the general formula (3) and various decylating agents. It is synthesized by a method of heating under an alkaline catalyst.

The decylating agent may be any of C1 to C4 alkyl decane or tri C1 to C4 alkyl decanolation or phenyl di C1 to C4 alkyl decane, and may be tri(C1 to C4 alkyl). The decylating agent is preferred. Preferred examples thereof include trimethylchlorodecane (TMCS), hexamethyldioxane (HMDS), and N,O-bis(trimethyldecyl) which are generally known as trimethylsulfonating agents. Trifluoroacetamide (BSTFA); or triethyl chlorodecane (TECS) as a triethyl decylating agent; tert-butyldimethyl decane (TBMS) as a third butyl dimethyl sulfonating agent Wait.

Such reagents can be easily obtained on the market by manufacturers such as hydrazine derivatives. The reaction amount (the alkylation equivalent) of the decylating agent is preferably 1.0 to 5.0 equivalents based on 1 equivalent of the hydroxyl group of tetraphenyl-1,2-ethanediol represented by the formula (3). It is more preferably 1.5 to 3.0 equivalents. When it is too small, the reaction efficiency is poor, and the reaction time becomes long to promote thermal decomposition. In addition, when it is too much, it is not easy to separate at the time of recycling, and it becomes difficult to refine.

The basic catalyst may, for example, be pyridine or triethylamine. The basic catalyst has an effect of trapping hydrogen chloride generated during the reaction, maintaining the reaction system in a basic state, or pulling a hydrogen atom of a hydroxyl group to further promote the reaction. The amount used is 1 equivalent of the hydroxyl group of the target compound, and the equivalent of the basic group may be 0.5 equivalent or more, and may be used as a solvent. Usually, the equivalent amount of the basic group of the basic catalyst is 1 to 5 equivalents based on 1 equivalent of the hydroxyl group of the target compound.

As the solvent, a nonpolar organic solvent such as hexane, diethyl ether or toluene is preferred because it does not participate in the reaction. Further, polar solvents such as pyridine, dimethylformaldehyde (DMF), dimethyl hydrazine (DMSO), tetrahydrofuran (THF), and acetonitrile are also preferred. Make The amount is preferably such that the weight concentration of the solute is from about 5 to 40% by mass. More preferably, it is 10 to 30% by mass. When too little, the reaction is slowed down, and the decomposition caused by heat is promoted to reduce the yield. In addition, when too much, the by-products are increased and the yield is reduced.

When the reaction temperature is introduced into a hydroxyl group of tetraphenyl-1,2-ethanediol of the general formula (3), it is preferably 80 ° C or less, and the reaction time is within 2.5 hours, preferably within 2 hours. . Since a tetraphenyl-1,2-ethaneglycol derivative such as tetraphenyl-1,2-ethanediol of the formula (3) or a target compound formed may cause thermal decomposition via heating, The low-temperature reaction is preferred. However, since it is a tertiary alcohol, it lacks reactivity. Therefore, it can be obtained in a high yield by reacting at 80 ° C or lower in a short time. If the reaction efficiency is also considered, it is preferably about 50 to 80 °C. The reaction time is from about 30 minutes to about 2.5 hours, preferably from about 30 minutes to about 2 hours.

When the decyl group is introduced into two hydroxyl groups of tetraphenyl-1,2-ethanediol of the formula (3), it is preferably a higher temperature, for example, a temperature of about 75 to 100 ° C, but the yield may be lowered.

The tetraphenylethane derivative represented by the formula (1) of the present invention can be used as a radical generating agent. Specifically, it can be used as a thermal radical generating agent or a photoradical generating agent in various fields, and in the present invention, it is particularly preferably used as a thermal radical generating agent.

The thermal radical generator of the present invention can also be used in applications where other photoradical generators are difficult to achieve. For example, it can be used for hardening of an unexposed portion or hardening of a portion where a strong energy is irradiated. Specifically, as a thermal radical generating agent in a sealant of a precision machine, it can be used as a A hard radical generating agent which hardens in a coexistence region of a low molecular substance which is decomposed, and can be used as a thermal radical generating agent for organic synthesis or the like caused by a thermal reaction. Further, the thermal radical generator of the present invention is not accompanied by foaming at the time of radical generation, and the curing rate is not impaired even in a small amount. Therefore, it is expected to maintain the shape of the cured product or enhance the physical properties. In the present invention, the amount of the radical generating agent of the tetraphenylethane derivative of the above formula (1) may be different depending on the type of the polymerizable monomer to be cured or the field of use, and the amount of addition may be appropriately selected. .

One of the preferred fields of use of the thermal radical generating agent of the present invention is used as a thermal radical generating agent 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 is not particularly limited, and is usually 0.1 to 10, based on the total amount of the composition. About % by mass. The remainder is a radically polymerizable resin and an additive contained as needed. The resin composition is cured by heat, and a cured product of the resin composition can be obtained. Since the cured product does not cause turbidity due to foaming, the transparency is good, and the adhesion, wet adhesion resistance, and the like are excellent. Further, examples of the radical curable resin include an epoxy resin and a (meth)acrylic resin. In particular, one of the useful radical curable resin compositions is, for example, a thermosetting sealant, and most preferably, it is a thermosetting liquid crystal sealant for a liquid crystal dropping method.

The thermosetting liquid crystal sealing agent for liquid crystal dropping method of the present invention contains (a) a tetraphenylethane derivative represented by the above formula (1), (b) an epoxy resin and/or an epoxy resin (A) The base acid acrylic acid adduct, (c) a thermal hardener, and (d) an inorganic filler are essential components.

The thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains (a) a tetraphenylethane derivative represented by the formula (1) as a thermal radical generating agent in order to improve the curability. The tetraphenylethane derivative represented by the following formula (1) is also referred to as a component (a) or a thermal radical generator (a) for the sake of simplicity.

The thermal radical generating agent generally means a compound which is dissociated by heating to generate a radical, and examples thereof include, for example, an azo compound, an organic peroxide, a benzoin, a benzoin ether, an acetophenone, and tetraphenyl-1,2. - Ethylene glycols, etc. However, an azo compound or an organic peroxide is foamed by generating a radical by heating while generating nitrogen gas, carbon dioxide, or the like. Therefore, air bubbles are contained in the hardened material, which causes deterioration of hardened physical properties and subsequent strength. In addition, the benzoin derivative, tetraphenyl-1,2-ethanediol, etc., do not foam when heated, but are used in the manufacture of a liquid crystal panel, at a temperature of about 90 to 130 ° C at a heat hardening temperature of the sealant. It is sufficiently pyrolyzed, so there is a problem that the desired degree of hardening cannot be obtained.

As a result of various reviews, the inventors of the present invention found that a thermal radical generating agent having high activity and low liquid crystal contamination can be obtained by chemically modifying tetraphenyl-1,2-ethanediol. Further, from the viewpoint of the ease of synthesis, it has been found that at least one of the hydroxyl groups of 2,3-dimethyl-2,3-butanediol (pinacol) forms an ether bond of tetraphenyl-1,2-B. A diol derivative. Examples of the ether bond include methyl ether, diethyl ether, propyl ether, diisopropyl ether, dibutyl ether, phenyl ether group, and decyl ether group. In the above, from the viewpoint of activity and the like, a phenyl ether group or a decyl ether group is preferred, and a tetraphenylethane derivative represented by the above formula (1) is more preferable.

The preferred tetraphenylethane derivative represented by the general formula (1) used in the present invention The substance (a) may, for example, be 1-hydroxy-2-di or tri(C1 to C4 alkyl) nonyloxy-1,1,2,2-tetraphenylethane or 1,2-double {di or Tris(C1 to C4 alkyl)decyloxy}-1,1,2,2-tetraphenylethane, 1-hydroxy-2-di or tri(C1 to C4 alkyl)decyloxy-1, 1,2,2-tetraphenylethane is more preferred, and more preferably 1-hydroxy-2-tris(C1 to C4 alkyl)decyloxy-1,1,2,2-tetraphenylethane . Specific compounds are as described above.

The thermal radical generating agent (a) (tetraphenylethane derivative (a) represented by the formula (1)) is preferably one in which the particle diameter is reduced and uniformly dispersed. When the average particle diameter is too large, when a liquid crystal cell having a narrow gap is formed, a gap or the like at the time of bonding the upper and lower glass substrates cannot be formed smoothly, which is a main cause of defects. Therefore, it is preferably 5 μm or less, and preferably 3 μm or less. Further, the particle diameter of the component (a) is not limited, and may be fine. However, the lower limit is usually about 0.1 μm.

In the liquid crystal sealing agent of the present invention, the content of (a) the thermal radical generating agent is usually 0.1 to 10% by mass, preferably 0.3 to 7% by mass, and 0.5 to 5% by mass based on the total amount of the liquid crystal sealing agent. % is preferred. When the content is too small, the hardenability is poor to cause a seal burst, and when the content is too large, the liquid crystal contamination tends to become strong.

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

The (meth)acrylic acid addition product (b) of the epoxy resin and/or 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. Here, "(meth)acrylic acid" means "propylene" Acid and/or "methacrylic acid". The (meth)acrylic acid addition product (b) of the epoxy resin and/or the epoxy resin is preferably one which has low contamination to the liquid crystal, low solubility, and low resin viscosity.

The epoxy resin is preferably exemplified by a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an ethylene oxide addition bisphenol S type epoxy resin, or a phenol (phenol). ) Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic acid varnish type epoxy resin, resorcinol diglycidyl ether, alicyclic Epoxy resin, aliphatic chain epoxy resin, glycidyl ether epoxy resin, glycidylamine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, Dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin having triphenol methane skeleton, bisglycidyl ether of other difunctional phenols, and other difunctional A diglycidyl ether compound of an alcohol or the like. These epoxy resins may be used singly or in combination of two or more. Among these, from the viewpoint of liquid crystal contamination and viscosity, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an ethylene oxide addition bisphenol S type epoxy resin, and the like are preferable. Hydroquinone diglycidyl ether, especially resorcinol diglycidyl ether is more preferred.

The (meth)acrylic acid addition product of the epoxy resin (hereinafter referred to as "(meth)acrylated epoxy resin") is a compound obtained by reacting an epoxy resin with (meth)acrylic acid. It may be a compound in which an epoxy group is added to a (meth)acrylic acid of an epoxy resin, or an epoxy group of an epoxy resin is deliberately left by reacting with an unsubstituted equivalent of (meth)acrylic acid. (hereinafter also referred to as a partial (meth)acrylated epoxy resin).

As the (meth) acrylated epoxy resin, a compound having a difunctional or higher (meth) acrylonitrile group is preferred. Further, the ratio of the epoxy group to the (meth) acrylonitrile group in the partially (meth) acrylated epoxy resin is not limited, and is appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

In the present invention, it is preferably 50 to 100%, preferably 70 to 100%, more preferably 80 to 100%, based on the total of the epoxy groups contained in the epoxy resin. (Meth)acrylated (meth)acrylated epoxy resin. In general, in (meth)acrylic acid, acrylic acid is often used from the viewpoint of inexpensiveness and the like. Therefore, it is preferred to use a compound in which an epoxy group of an epoxy resin is added with an acrylic acid.

The epoxy resin which is a raw material of the (meth)acrylated epoxy resin is not particularly limited, and a difunctional or higher epoxy resin is preferred.

For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, ethylene oxide addition bisphenol S epoxy resin, phenol novolak epoxy resin, Cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, resorcinol diglycidyl ether, alicyclic epoxy resin, aliphatic chain ring Oxygen resin, glycidyl ether type epoxy resin, glycidylamine type epoxy resin, ethyl uret urea type epoxy resin, isocyanurate type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl A type epoxy resin, a phenol novolak type epoxy resin having a trisphenol methane skeleton, a di-glycidyl ether compound of another difunctional phenol, and a diglycidyl ether compound of another difunctional alcohol.

It is better to use bisphenol A epoxy resin, bisphenol F epoxy resin or resorcinol diglycidyl ether, especially resorcinol diglycidyl ether. good.

Therefore, as the (meth) acrylated epoxy resin, at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and resorcin diglycidyl ether The (meth)acrylated epoxy resin obtained by reacting (meth)acrylic acid is preferred, and the (meth)acrylated epoxy resin obtained by reacting resorcinol diglycidyl ether with (meth)acrylic acid is Better.

As the (meth) acrylated epoxy resin, an acrylated epoxy resin obtained by reacting an epoxy resin with acrylic acid is preferred from the viewpoint of curability. Preferably, at least one 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 resorcinol diglycidyl ether .

The (meth)acrylated epoxy resin may be used singly or in combination of two or more.

In a preferred embodiment, the above preferred (meth)acrylated epoxy resin accounts for the entire amount of the (meth)acrylated epoxy resin in the liquid crystal sealant.

In the liquid crystal sealing agent of the present invention, the content of the epoxy resin and/or the (meth)acrylated epoxy resin (b) (hereinafter simply referred to as the curable resin (b)) is relative to the total amount of the liquid crystal sealing agent. It is usually 30 to 75% by mass, preferably 40 to 65% by mass. When the content is too small, the reaction at the time of heat hardening becomes slow. When the liquid crystal cell is formed in the liquid crystal dropping method, the bank of the sealant is caused to leak due to thermal expansion of the liquid crystal and low viscosity of the sealant. When the content is too large, sufficient bonding strength cannot be obtained.

As the curable resin (b), epoxy resin and (meth) acrylated The aspect of both of the epoxy resins is one of the preferred aspects of the sealant of the present invention.

Further, in particular, in the case where the epoxy resin is used in combination with the (meth)acrylated epoxy resin, the epoxy resin content in the curable resin (b) is usually 3 to the total amount of the curable resin (b). 40% by mass is preferably 3 to 30% by mass, preferably about 5 to 30% by mass, more preferably 8 to 30% by mass. Further, depending on the case, it 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 resin is 60 to 97% by mass, preferably 70 to 95% by mass, and 70 to 92% by mass based on the total amount of the curable resin (b). % is better. When the epoxy resin content is too small, the bonding strength is weakened, and when the epoxy resin content is too large, the hardening becomes slow, and it is likely that a seal burst is likely to occur.

The thermosetting liquid crystal sealing agent for a liquid crystal dropping method of the present invention contains a thermosetting agent (c). As the heat hardener (c), any one of conventionally used heat hardeners can be used, but in the present invention, a latent heat hardener (hereinafter also referred to as a latent heat hardener) is preferred. The latent heat curing agent is a compound having a melting point or a softening point of a solid at a temperature of 100 ° C or higher at room temperature, and does not react with the resin component at room temperature, and does not function as a hardening agent, and is heated to 100 ° C or higher, usually 100 to It is about 150 ° C, preferably about 110 to 130 ° C, slowly dissolves or melts to react with the resin component, and acts as a hardener.

Further, in the present invention, the melting point or softening point is measured by thermal analysis using a differential scanning calorimeter (DSC). Specifically, a differential scanning calorimeter (EXSTAR 6000, manufactured by Seiko Instruments Co., Ltd.) was used to measure the temperature by 5 ° C per minute.

Examples of the latent curing agent include a polyhydrazide compound, a polyamine compound, an imidazole derivative, and a urea derivative. A polyfluorene derivative is preferred, and is a compound having two or more mercapto groups in the molecule. Preferably, two to four hydrazine compounds are preferred, and two or three hydrazine compounds are more preferred.

Examples of the polyfluorene compound include, for example, diterpene oxalate, diammonium malonate, diterpene succinate, diammonium adipate, diammonium pimelate, dinononate, and bismuth suberate. Bismuth azelaic acid, diterpene sebacate, dinonyl dodecanoate, dihexadecane hexanoate, diterpene maleate, dioxane fumarate, oxydiacetate Bismuth, bismuth tartrate, diterpene malate, diterpene bismuth, diterpene bismuth, diammonium 2,6-naphthalene dicarboxylate, 4,4-bisbenzoquinone, 1 , 4-naphthalene dicarboxylate, 2,6-pyridine dioxime, 1,2,4-benzenetriazole, pyromellitic tetraruthenium, 1,4,5,8-naphthoic acid tetraquinone乙; having an intramethylene uregar skeleton such as 1,3-bis(hydrazinocarbonoethyl-5-isopropylhydantoin), preferably 缬Amino acid carbendazim skeleton (a skeleton in which the carbon atom of the uremone ring is substituted with an isopropyl group); gin (1-mercaptocarbonylmethyl) isocyanurate, ginseng (2-mercaptocarbonylethyl) ) isocyanurate, ginseng (3-mercaptocarbonylpropyl) isocyanurate, bis(2-mercaptocarbonylethyl) isocyanurate, etc. Ylcarbonyl C1 to C3 alkyl) isocyanurate, these can be used singly or two or more kinds may be mixed. Bis- or hydrazino (fluorenylcarbonyl C1 to C3 alkyl) isocyanurate is one of the preferred compounds as a di- or tri-quinone compound.

Among these polyvalent compounds, two or three of the di or tricarboxylic acids are preferred. 肼, more specifically, a di- or di- or bis(nonylcarbonyl C1 to C3 alkyl) isocyanuric acid of a C4 to C8 aliphatic or aromatic dicarboxylic acid, in addition to a carbon of a carboxylic acid The acid ester or the like is preferably at least one selected from the group consisting of diterpenes of C4 to C8 alkanoic acid, diterpene bismuth, and thioxylcarbonyl C1 to C3 alkyl isocyanurate. .

Preferred examples of the polyhydrazine include, for example, diammonium adipate, diterpene sebacate, diterpene niobate, and 1,3-bis(carbazinoethyl)-5-iso Propyl carbendazim, ginseng (1-mercaptocarbonylmethyl) isocyanurate, ginseng (2-mercaptocarbonylethyl) isocyanurate, ginseng (3-mercaptocarbonylpropyl) Cyanurate, bis(2-mercaptocarbonylethyl) isocyanurate.

More preferably, it is exemplified by diammonium adipate, diterpene sebacate, diammonium phthalate, and bis(2-mercaptocarbonylethyl) isocyanurate.

In order to act as a latent hardening agent, the heat hardener (c) is preferably one in which the particle diameter is made fine and uniformly dispersed. When the average particle diameter is too large, when a liquid crystal cell having a narrow gap is produced, a gap or the like cannot be formed smoothly when the upper and lower glass substrates are bonded together, which may cause a defect. Therefore, the particle diameter is preferably 4 μm or less, and preferably 3 μm or less. The particle diameter was measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishin Co., Ltd.: LMS-30). Further, when the average particle diameter is too small, aggregation tends to occur, and it is preferable to prepare a method which is not extremely small (for example, 0.1 μm or less).

In the liquid crystal sealing agent of the present invention, the content of the thermosetting agent (c) is usually 5 parts by mass based on 100 parts by mass of the curable resin (b) as the epoxy resin or the (meth)acrylated epoxy resin. It is preferably from 10 parts by mass to 40 parts by mass, based on about 60 parts by mass. When the thermal hardener (c) is less than 5 parts by mass, The heat hardening reaction becomes insufficient, and the force and glass transition point become lower. On the other hand, when the thermal curing agent exceeds 60 parts by mass, the curing agent remains so that the adhesion force is lowered, and in addition, the use period is also deteriorated.

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 alumina, cerium oxide (spherical cerium oxide or fumed silica, etc.), talc, clay, bentonite, organic bentonite, and titanic acid. Metal oxides such as barium, titanium oxide, cobalt oxide, magnesium oxide, nickel oxide, and zirconium oxide; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; metal hydroxides such as aluminum hydroxide and magnesium hydroxide Lithium citrate, aluminum citrate, zirconium citrate and the like. These may be used alone or in combination of two or more. Among these inorganic fillers, alumina and/or cerium oxide are particularly preferred.

The inorganic filler (d) preferably has an average particle diameter of 3 μm or less.

When the average particle diameter is too large, the formation of a gap when the liquid crystal cell is bonded to the upper and lower glass substrates is hindered. The lower limit of the average particle diameter of the inorganic filler (d) is usually about 0.01 μm.

In the liquid crystal sealing agent of the present invention, the content of the inorganic filler (d) is usually from 1 to 30% by mass, preferably from 2 to 20% by mass, more preferably from 3 to 15% by mass. When the content is too small, the adhesion strength to the glass substrate is lowered. Further, when the content of the filler is too large, the viscosity is too high to deteriorate the coatability.

The liquid crystal sealing agent of the present invention contains a hardening accelerator (e) for promoting the hardenability of the thermosetting reaction.

As the curing accelerator, it is possible to improve the heat hardening reaction promoting property during heating, to have low contamination to liquid crystals, and to prevent liquid crystal sealing agent from being stored at normal temperature. There is no particular limitation on the deterioration of the use period.

For example, a polyvalent carboxylic acid or an epoxy resin amine adduct having an isocyanuric acid ring skeleton, an imidazole derivative, a urea derivative, or the like can be given. These may be used alone or in combination of two or more. As a preferable hardening accelerator, a urea compound hardening accelerator or a polycarboxylic acid hardening accelerator containing an isocyanuric acid ring skeleton can be mentioned. Specifically, an aliphatic dimethyl urea (trade name: UCAT3503N, manufactured by San-Apro Co., Ltd.) (a compound in which a continuous position on a cyclohexane ring is substituted with a methyl group and two dimethylureido groups), and aroma Group of dimethylurea (trade name: UCAT3502T, manufactured by San-Apro Co., Ltd.) (compound substituted with 2 dimethylureido groups at the 2 and 3 positions of toluene), ginseng (carboxy C1 to C3 alkyl group) Cyanurate. Examples of the ginic (carboxy C1 to C3 alkyl) isocyanurate include ginseng (1-carboxymethyl) isocyanurate, ginseng (2-carboxyethyl) isocyanurate, and ginseng ( 3-Carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate. Among them, ginseng (3-carboxypropyl) isocyanurate is preferred.

The hardening accelerator (e) is preferably used as a latent curing accelerator for speed hardening to make the particle diameter fine and uniformly dispersed. When the average particle diameter is too large, when a liquid crystal cell having a narrow gap is produced, it is not possible to form a gap or the like when the upper and lower glass substrates are bonded together, which may cause a defect. Therefore, the average particle diameter is preferably 4 μm or less, and preferably 3 μm or less. The lower limit of the average particle diameter is usually about 0.1 μm.

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

When the content is too small, the hardenability deteriorates to cause a seal burst, and when the content is too large, the stability at room temperature and the linearity of the seal become poor.

A coupling agent (f) may also be added to the liquid crystal sealing agent of the present invention to increase the bonding strength. The coupling agent (f) is not specifically limited.

Examples of the coupling agent (f) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, N-phenyl-γ-aminopropyltrimethoxydecane, N-(2-amine Benzyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl) 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3 a decane coupling agent such as methacryloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; isopropyl (N-ethylamine) Base ethylamino) titanate, isopropyl triisooctadecanoyl titanate, titanium (dioctyl pyrophosphate) oxyacetate, tetraisopropyl bis (dioctyl phosphite) a titanium-based coupling agent such as titanate or neoalkoxyl tris(p-N-(β-aminoethyl)aminophenyl) titanate; Zr-acetonitrile Acid salt, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy neodecyl zirconate, neoalkoxy(dodecyldecyl)benzene Zirconium coupling agent such as sulfonyl zirconate, neoalkoxy (ethylenediamine ethyl) zirconate, neoalkoxy (m-aminophenyl) zirconate, ammonium zirconium carbonate; Al An aluminum coupling agent such as acetaminophenate, Al-methacrylate or Al-propionate may be used alone or in combination of two or more.

Among these coupling agents, a decane coupling agent is preferred, and an amine decane coupling agent or an epoxy decane coupling agent is more preferred.

By using the coupling agent, a liquid crystal sealing agent which is excellent in moisture resistance reliability and which has reduced moisture absorption and subsequent strength reduction can be obtained. When the coupling agent is contained in the liquid crystal sealing agent of the present invention, the content thereof is about 0.05 to 3% by mass.

The liquid crystal sealing agent of the present invention may further contain a polythiol compound (g) for further improving the hardenability. As the polythiol compound, a compound having two or more thiol groups in the molecule is preferred. Examples thereof include methyl dithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, and 1,2,3-trimethylpropane. , 1,4-didecylbutane, 1,6-dimercaptohexane, bis(2-mercaptoethyl) sulfide, 1,2-bis(2-mercaptoethylthio)ethane, 1,5- Dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethyl Oxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-didecylbutane, 2-(2-mercaptoethylsulfide -1,3-dimercaptopropane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,1,1-paraxyl (mercaptomethyl)propane, anthracene (fluorenylmethyl) Methane, ethylene glycol bis(2-mercaptoacetic acid) ester, ethylene glycol bis(3-mercaptopropionic acid) ester, 1,4-butanediol bis(2-mercaptoacetic acid) ester, 1,4-butanediol Bis(3-mercaptopropionic acid) ester, trimethylolpropane ginseng (2-mercaptoacetic acid) ester, trimethylolpropane ginseng (3-mercaptopropionic acid) ester, pentaerythritol bismuth (2-mercaptoacetic acid) ester, pentaerythritol肆(3-mercaptopropionic acid) ester, 1,1-dimercaptocyclohexane, 1,4-dioxylcyclohexane, 1,3-didecylcyclohexane, 1,2-di Cyclohexane, dipentaerythritol tert- (trimercaptopropionate), dipentaerythritol tert-(mercaptoacetic acid) ester, 1,2-mercaptobenzene, 1,3-dimercapto-2-propanol, 2,3 -dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, hydroxymethyl-parade(mercaptoethylthiomethyl)methane, hydroxyethylthiomethyl-paraben Thio)methane, ethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), butanediol bis(3-mercaptopropionate), octanediol bis(3-mercapto) Propionate), tetraethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(4-mercaptobutyrate), propylene glycol bis(4-mercaptobutyrate), butanediol bis (4- Mercaptobutyrate), octanediol bis(4-mercaptobutyrate), trimethylolpropane ginseng (4-mercaptobutyrate), pentaerythritol bis(4-mercaptobutyrate), ethylene glycol bis ( 6-mercaptovalerate, propylene glycol bis(6-mercaptovalerate), butanediol bis(6-mercaptovalerate), octanediol bis(6-mercaptovalerate), trimethylolpropane Ginseng (6-mercapto-valeric acid) ester, pentaerythritol bismuth (6-mercapto valerate), 1,6-hexanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 4, 4'-bis(decylmethyl)phenyl sulfide, 2,4'-bis(fluorenyl) Phenyl thioether, 2,4,4'-tris(decylmethyl)phenyl sulfide, 2,2',4,4'-tetrakis(fluorenylmethyl)phenyl sulfide, 1,3, 5-parat[2-(3-mercaptopropenyloxy)ethyl]-1,3,5-three -2,4,6(1H,3H,5H)-trione, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, pentaerythritol ruthenium (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy)butane, which can be used alone It can be used in combination of 2 or more types.

Among these polythiol compounds, trimethylolpropane ginseng (3-mercaptopropionic acid) ester, pentaerythritol bismuth (2-mercaptoacetic acid) ester, dipentaerythritol tert-(mercaptopropionic acid) ester, 1,3 ,5-[2-(3-amidinopropyloxy)ethyl]-1,3,5-three -2,4,6(1H,3H,5H)-trione, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, pentaerythritol ruthenium (3-mercaptobutyrate), preferably, from the viewpoint of liquid crystal contamination and room temperature storage stability, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-three with a 2-stage thiol structure -2,4,6(1H,3H,5H)-trione, pentaerythritol ruthenium (3-mercaptobutyrate) is particularly preferred.

When the polythiol compound (g) is contained in the thermosetting liquid crystal sealing agent for liquid crystal dropping method of the present invention, the content thereof is usually from 0.1 to 10% by mass, preferably from 0.3 to 5% by mass. When the content is too small, the hardenability is deteriorated, and the seal burst is likely to occur. When the content is too large, the room temperature storage stability is likely to deteriorate.

In the thermosetting liquid crystal sealing agent for liquid crystal dropping method of the present invention, the organic filler (h) may be added to the extent that the characteristics of the liquid crystal sealing agent are not affected. Examples of the organic filler (h) include silicone gum fine particles, acrylic rubber fine particles, and core-shell type acrylic fine particles. These organic fillers may be used singly or in combination of two or more.

The organic filler to be added has an average particle diameter of usually 5 μm or less, preferably 2 μm or less. When the average particle diameter is too large, it is difficult to form a cell gap. However, when the organic filler is a silicone rubber powder, even if the average particle diameter is large, a cell gap can be formed, so that the preferred average particle diameter of the silicone rubber powder is 15 μm or less.

In addition, when the organic filler is contained in the liquid crystal sealing agent of the present invention, the content thereof is preferably 40% by mass or less, and preferably 30% by mass or less based on the total amount of the liquid crystal sealing agent. The lower limit may be 0% by mass. In general, it is preferably 1% by mass or more, and preferably 5% by mass or more. When it is too much, the viscosity becomes high and it is difficult to form a cell gap. The liquid crystal encapsulant of the present invention contains one of the preferred aspects of the organic filler.

In addition, as an organic filler, use neodymium rubber particles and other The organic filler, for example, a (meth)acrylic resin microparticle (preferably a core-shell type (meth)acrylic microparticle) is also one of preferred aspects of the invention. In this case, the silicone rubber fine particles are usually used in a ratio of from 1 to 10 parts by mass, preferably from 3 to 7 parts by mass, based on 1 part by mass of the other organic filler.

The liquid crystal sealing agent of the present invention may further contain an additive such as a photoradical polymerization initiator, an organic solvent, a pigment, a leveling agent, or an antifoaming agent, as needed.

The following are a few preferred aspects of the sealant of the present invention.

1. The invention according to any one of (5) to (14), wherein the curable resin (b) is a combined epoxy resin and (a) Base) acrylated epoxy resin.

2. The aspect as described in the above 1, wherein the content of the epoxy resin is from 3 to 40% by mass based on the total amount of the curable resin (b), and the content of the (meth)acrylated epoxy resin is 60. Up to 97% by mass.

3. The aspect of the invention according to (11) to (14) of the above (1) to (5) to (14), wherein the invention of the above-mentioned 1 or 2 contains the hardening accelerator (e), wherein The content of the hardening accelerator is from 0.5 to 15% by mass, preferably from 1 to 8 by mass, based on the total amount of the sealant of the present invention.

4. The aspect as described in the above 3, wherein the curing accelerator (e) is a polycarboxylic acid hardening accelerator containing an isocyanuric acid ring skeleton.

5. The aspect as described in 4 above, wherein the hardening accelerator (e) is a gin (carboxy C1 to C3 alkyl) isocyanurate.

6. The aspect as recited in any one of items 1 to 5 above, which contains the above The invention of the coupling agent (f) according to any one of (1) to (14) to (14), wherein The total amount of the sealant and the coupling agent (f) are from 0.05 to 3% by mass.

7. The aspect as described in the above 6, wherein the coupling agent (f) is a decane coupling agent.

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

9. The aspect as described in any one of the above 1 to 8, wherein the organic filler (h) is further contained in an amount of from 1 to 40% by mass based on the total amount of the sealant of the present invention.

In order to obtain the liquid crystal sealing agent of the present invention, the epoxy resin and/or (meth)acrylated epoxy resin (b), if necessary, a mixed coupling agent or an additive is dissolved, and the above-mentioned heat hardener is appropriately added thereto. (c), the thermal radical generating agent (a), the inorganic filler (d), the hardening accelerator (e), and other optional components, such as three rolls, a sand mill, or the like by a usual mixing device A ball mill or the like can be uniformly mixed. It is preferred to carry out a filtration treatment for removing foreign matter after the completion of the mixing.

In the liquid crystal display unit of the present invention, one of the predetermined electrodes is formed to face the substrate at a predetermined interval, and is sealed with a liquid crystal sealing agent of the present invention, and a liquid crystal is sealed in the gap. The type of the liquid crystal to be sealed is not particularly limited.

Here, the substrate is made of glass, quartz, plastic, tantalum or the like. In the method for producing a liquid crystal display unit in the thermosetting liquid crystal dropping method, first, a spacer (control gap material) such as glass fiber is added to the liquid crystal sealing agent of the present invention and mixed. As a spacer, for example, Glass fiber, cerium oxide beads, polymer beads, and the like. The diameter thereof is different from the purpose, and is usually 2 to 8 μm, preferably 3 to 6 μm, and is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent. It is preferably from about 0.9 to 1.5 parts by mass.

After the liquid crystal sealing agent prepared with the spacer is applied to one side of the substrate via a dispenser or the like to form a bank (main seal), in order to hold the liquid crystal sealing substrate in a vacuum, a sealant is applied over one of the outermost periphery (pseudo seal). Subsequently, the liquid crystal was dropped on the inside of the inner sealed bank, and after bonding another glass substrate in a vacuum, the gap was formed by releasing to atmospheric pressure. The pseudo-sealant for holding the liquid crystal sealing substrate in a vacuum is not in contact with the liquid crystal, and since it is cut off after the liquid crystal cell is completed, the same liquid crystal sealing agent can be used, and other UV hardening type sealing agents can be used. Visible light hardening type sealant or thermosetting sealant. After the vacuum gap is formed, when a UV curable sealant or a visible light curable sealant is used as the photocurable sealant in the pseudo seal, the pseudo seal portion is hardened by irradiating the pseudo seal portion with ultraviolet rays or visible light via an ultraviolet irradiator or a visible light irradiation device. . When the photo-curing type sealant is not used for the pseudo seal, the light irradiation step can be omitted. The substrate on which the gap is formed is heated at 90 to 130 ° C for 1 to 2 hours, and then, the liquid crystal display unit of the present invention can be obtained by cutting the dummy seal portion.

The liquid crystal display unit of the present invention thus obtained is free from display defects caused by liquid crystal contamination, and is excellent in adhesion and moisture resistance.

[Examples]

The invention will now be described in more detail by way of examples.

Further, the present invention is not limited to the following embodiments.

In the examples, unless otherwise specified, parts mean parts by mass and % means mass%.

[Example A] [Synthesis of 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane] (decylated tetraphenyl-1,2-ethanediol)

100 parts (0.28 mol) of commercially available tetraphenyl-1,2-ethanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformaldehyde. Here, 32 parts (0.4 mol) of pyridine as a base catalyst, and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a decylating agent were added, and the mixture was heated to 70 ° C and stirred for 2 hours. The obtained reaction liquid was cooled, and 200 parts of water was added thereto with stirring to precipitate a product and passivate the unreacted decylating agent. The precipitated product was separated by filtration and washed thoroughly with water. Next, the obtained product was dissolved in acetone, rehydrated by adding water, and then purified. 105.6 parts of 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane as a target was obtained (yield 88.3%).

As a result of analysis by HPLC (High Performance Liquid Chromatography), the purity was 99.0% (area percentage).

A molecular ion peak of 438 was obtained via HPLC-MASS (High Performance Liquid Chromatography-Mass Analysis). Further, hydroxyproton 5.8 ppm (1H), decyloxymethyl proton 0.0 ppm (9H), phenyl proton 7.1 ppm (16H), and 7.4 ppm were obtained as chemical shift values from the NMR spectrum (solvent DMSO-d ₆ ). (4H), confirmed as the subject matter. The NMR spectrum is shown in Fig. 1.

Further, since the tetraphenyl-1,2-ethanediol derivative has a reactivity due to a large steric hindrance due to a large steric hindrance, one of the two tertiary alcohols is considered to be selective in the above reaction. The ground is introduced into the decyl group.

[Experimental Example 1]

In order to observe the effect of the thermal radical generator of the present invention, the gelation time of the sample at 120 ° C (time of hardening on a hot plate at 120 ° C) and a foaming test were carried out.

(experiment method)

10 parts of an acrylic acid addition product (manufactured by Nippon Kayaku Co., Ltd.: R93100) of bisphenol A type epoxy resin, and 0.1 part of each of them as a thermal radical generating agent, Test Example 1 (present invention) 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, Test Example 2 (comparative) tetraphenyl-1,2-ethanediol, test example 3 (comparative) is a tributyl butyl peroxy-2-ethylhexanoate (Kayaester O, manufactured by Akzo Co., Ltd.), and the respective samples were adjusted by kneading through three rolls.

The obtained sample was placed on a hot plate at 120 ° C for hardening time (gelation time at 120 ° C) and visually observed whether or not the cured product was turbid due to foaming. The results are shown in Table A. Further, the curing time was such that the sample was contacted with a glass rod and the time until the sample was not drawn was measured.

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

Evaluate whether there is turbidity due to foaming

○: The cured product was not turbid and was transparent due to foaming.

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

×: It was confirmed that the entire cured product was white and cloudy due to foaming, and the transparency was also remarkably lowered.

As shown in Table A, the thermal radical generator (Test Example 1) of the present invention has a high curing rate, no foaming, and no turbidity, and is therefore also suitable for various applications requiring transparency.

On the other hand, in Test Example 2 as a comparison object, although there was no problem in transparency, the curing time was long and there was a problem of workability, and Test Example 3 was excellent in the characteristics of the curing time, but turbidity due to foaming was caused. The transparency is deteriorated, and it is not suitable for applications requiring transparency, and further, there is a concern that the physical properties of the cured product are lowered by foaming.

[Examples 1, 2, Comparative Examples 1, 2]

The acrylated epoxy resin, epoxy resin, and decane coupling agent described in Table 1 below were mixed to obtain a resin liquid.

In the obtained resin liquid, the inorganic filler, the heat hardener, the hardening accelerator, the decaneated tetraphenyl-1,2-ethanediol, the polythiol compound, and the oxirane rubber are respectively prepared according to the amounts described in Table 1. The powder (organic filler) and the core-shell acrylic fine particles (organic filler) were kneaded by three rolls to obtain liquid crystal sealants of Examples 1 and 2.

In the composition of the above Example 1, except that tetraphenyl-1,2-ethanediol was used in an amount as described in Table 1, the tetraalkyl-1,2-ethanediol was substituted, and the same as in the examples. The liquid crystal sealing agent of Comparative Example 1 was obtained.

Further, in the composition of Example 1, the liquid crystal of Comparative Example 2 was obtained in the same manner as in Example 1 except that the amount of the organic peroxide described in Table 1 was used instead of the decylated tetraphenyl-1,2-ethanediol. Sealants.

[Reference Synthesis Example 1] [Synthesis of a full acrylate of resorcinol diglycidyl ether]

140 parts of resorcinol diglycidyl ether resin was dissolved in 160 parts of toluene. 0.48 parts of dibutylhydroxytoluene as a polymerization inhibiting agent was added thereto, and the temperature was raised to 60 °C. Subsequently, 100 parts of acrylic acid (100% equivalent of epoxy group of resorcin diglycidyl ether resin) was added, and the temperature was raised to 80 ° C, and 0.96 parts of trimethylammonium chloride as a reaction catalyst was added thereto. Stir at 98 ° C for about 50 hours. The obtained reaction liquid was washed with water, and the toluene was distilled off to obtain 241 parts of an epoxy acrylate of resorcin.

The values in Table 1 are parts by weight.

*1: Total acrylate of resorcinol diglycidyl ether (refer to the compound obtained in Synthesis Example 1)

*2: Resorcinol diglycidyl ether (manufactured by Nippon Kayaku Co., Ltd., trade name: RGE-HH)

*3: Spherical yttrium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-24-9163A; primary average particle diameter: 110 nm)

*4: Neodymium rubber powder (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KMP-598; primary average particle size 13 μm)

*5: 3-glycidoxypropyltrimethoxydecane (manufactured by Chisso Co., Ltd., trade name: SILA-ACE ^RTM S-510)

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

*7: ginseng (2-mercaptocarbonylethyl) isocyanurate finely pulverized product (manufactured by Japan Finechem Co., Ltd., trade name: HCIC, finely pulverized by a jet mill to an average particle diameter of 1.5 μm)

*8: 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane (a compound obtained in the same manner as in Example A (decylated tetraphenyl-1, 2) -Glycol) is finely pulverized by a jet mill to an average particle diameter of 1.9 μm)

*9: Tetraphenyl-1,2-ethane glycol finely pulverized product (a tetraphenyl-1,2-ethylene glycol manufactured by Tokyo Chemical Industry Co., Ltd. was finely pulverized by a jet mill to an average particle diameter of 1.9 μm)

*10: tert-butyl peroxy 2-ethylhexanoate (manufactured by Akzo Co., Ltd., trade name: Kayaester ^RTM O)

*11: Pentaerythritol 肆(3-mercaptobutyric acid) ester (manufactured by Showa Denko Co., Ltd., trade name: Karenz ^RTM MT PE1)

*12: ginseng (3-carboxypropyl) isocyanurate pulverized product (manufactured by Shikoku Chemicals Co., Ltd., trade name: C3-CIC acid, finely pulverized by a jet mill to an average particle size of 1.5 μm)

*13: Core-shell acrylic microparticles (manufactured by Ganz Chemical Co., Ltd., trade name: F351S; average particle diameter 0.3 μm)

[Production evaluation liquid crystal unit]

1 g of 5 μm glass fiber as a separator was added to 100 g of each of the liquid crystal sealing agents of Examples 1 and 2 or Comparative Examples 1 and 2, and the mixture was stirred and defoamed, and filled in a syringe. An oriented film solution (trade name: PIA-5540-05A, manufactured by Chisso Co., Ltd.) was applied to a glass substrate with an ITO transparent electrode, and after calcination, rubbing treatment was performed. In this substrate, a sealing pattern and a pseudo-sealing pattern were formed using a dispenser (SHOTMASTER 300: manufactured by Musashi Engineering Co., Ltd.) in each of the liquid crystal sealing agents of the examples and the comparative examples which were previously filled in the syringe, and then the liquid crystal (trade name: JC) The droplets of -5015LA, manufactured by Chisso Co., Ltd.) were dropped in the frame of the seal pattern. In addition, the glass substrate spread surface spacer (trade name: Natoco-Spacer KSEB-525F, manufactured by Natoco Co., Ltd., gap width: 5 μm after bonding) was subjected to heat treatment, and vacuum was used. The bonding device is bonded to the substrate on which the liquid crystal is dropped in advance in a vacuum. Subsequently, after releasing into the atmosphere to form a gap, it was placed in a 120 ° C oven and heat-hardened for 1 hour to prepare a liquid crystal test unit for evaluation.

Table 2 shows the results of the sealing shape of the liquid crystal cell for evaluation and the liquid crystal orientation dispersion observed by a polarizing microscope. In addition, the results of measurement of the gap of the liquid crystal cell produced by the liquid crystal cell evaluation apparatus (trade name: OMS-NK3, manufactured by Central Seiki Co., Ltd.) are shown in Table 2. The seal shape, the liquid crystal orientation dispersion, and the evaluation of the liquid crystal cell gap are the following four stages.

[Evaluating Seal Shape]

○: The linearity of the seal is not scattered.

△: It was judged that the seal was deformed, but the liquid crystal seal was not problematic.

X: The liquid crystal is infiltrated in the seal, and the sealing of the liquid crystal may cause a problem.

××: The liquid crystal collapsed and the unit could not be formed.

[Evaluating Liquid Crystal Cell Gap]

○: The cell gap was uniformly 5 μm in the cell.

△: There is a cell gap of about 5.5 μm in the cell.

×: There is a cell gap of 6 μm or more in the cell.

××: The liquid crystal collapsed and the unit could not be formed.

[Evaluating liquid crystal orientation]

○: The orientation of the liquid crystal close to the seal is not scattered.

△: The orientation of only a few areas close to the seal is scattered.

×: There is a directional dispersion from the seal to the wide area.

××: The liquid crystal collapsed and the unit could not be formed.

[Liquid Crystal Sealant Strength Test]

In the liquid crystal sealing agents of 100 g each of Examples 1, 2 or Comparative Examples 1 and 2, 1 g of 5 μm glass fiber as a separator was added and mixed and stirred. This liquid crystal sealing agent was applied onto a glass substrate of 50 mm × 50 mm, and a glass piece of 1.5 mm × 1.5 mm was attached to the liquid crystal sealing agent, and placed in an oven at 120 ° C for 1 hour to be hardened. The shear strength of this glass piece was measured using a Bond Tester (trade name: SS-30WD, manufactured by Sejin Corporation). The results are shown in Table 3 below.

[Liquid sealant moisture resistance strength test]

A measurement sample similar to the above-described liquid crystal sealant adhesion strength test was prepared. The measurement sample was placed in a pressure cooker tester (trade name: TPC-411, manufactured by Tabai Espec Co., Ltd.) at 121 ° C, 2 atm, and 100% humidity for 20 minutes, using Bond Tester (trade name: SS- 30WD, manufactured by Xijin Commercial Co., Ltd.). The results are shown in Table 3 below.

[Period of use]

The viscosity change of the obtained liquid crystal sealing agent at 25 ° C was measured using an R type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). The % increase rate of viscosity with respect to the initial viscosity is shown in Table 3 below.

As shown in Tables 2 and 3, the liquid crystal sealing agent of the embodiment of the present invention using decylated tetraphenyl-1,2-ethanediol as a radical generating agent was used as compared with Comparative Example 1 using tetraphenyl-1. 2-Glycol as a radical generator is remarkably superior in any of the characteristics of liquid crystal orientation, adhesion strength, and moisture resistance.

(industrial availability)

According to the above, the tetraphenylethane derivative of the present invention has high gelation time and no foaming in the composition as a radical curable resin because of its high radical generating property through heat and no foaming. Thermal free radical generator. Further, since the transparency is not lowered by foaming or the physical properties of other cured materials are lowered, a cured resin having high transparency and good physical properties can be obtained. Further, when the tetraalkylethane derivative is used as a thermal radical generator in a liquid crystal sealing agent, the sealant liquid crystal is less polluting and has a long service life. Since the formability of the seal and the formability of the gap are also good, workability is also good, and further, the strength and the wet strength are excellent after the joint strength. Therefore, it is suitable for use as a thermosetting liquid crystal sealing agent for liquid crystal dropping methods.

Since the picture in this case is experimental data, it is not a representative figure of this case.

Therefore, there is no designated representative map in this case.

Claims (8)

a tetraphenylethane derivative represented by the following formula (1'), (wherein, Y ^{1 '} or Y ^{2 '} each independently represents a hydrogen atom or a halogen 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, X ¹ to X ⁴ each independently represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom; however, either Y ^{1 '} or Y ^{2 '} is a hydrogen atom, and the other is A halogen atom, when Y ^{1 '} or Y ^{2 '} is a hydrogen atom, R ¹ to R ³ or R ⁴ to R ⁶ are absent). The tetraphenylethane derivative according to claim 1, wherein one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other represents a halogen atom, Y ^{When 1'} or Y ^2' is a ruthenium atom, R ¹ R ² R ³ Y ^1' - or R ⁴ R ⁵ R ⁶ Y ^2' - is a bis (linear or branched alkyl group having 1 to 4 carbon atoms) decyl group Or tris (straight or branched alkyl having 1 to 4 carbon atoms) decyl group, and X ¹ to X ⁴ are each a hydrogen atom. The tetraphenylethane derivative according to claim 1, wherein one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other represents a halogen atom, Y ^{When 1'} or Y ^{2 '} is a halogen atom, R ¹ R ² R ³ Y ^1' - or R ⁴ R ⁵ R ⁶ Y ^2' - is trimethyldecyl, triethyldecyl or tert-butyl Methyl decyl group, and X ¹ to X ⁴ are all hydrogen atoms. The tetraphenylethane derivative according to claim 1, which is 1-hydroxy-2-trimethyldecyloxy-1,1,2,2- represented by the following formula (2). Tetraphenylethane A radical generating agent comprising the tetraphenylethane derivative of the formula (1') according to any one of claims 1 to 4 as an active ingredient. A cured product obtained by thermally hardening a radical curable resin composition containing a tetraphenylethane derivative of the formula (1') according to any one of claims 1 to 4; Winner. A process for producing a tetraphenylethane derivative represented by the following formula (1') which is a tetraphenyl-1,2-ethanediol represented by the following formula (3) and a decylating agent Reacted, (wherein, Y ^{1 '} or Y ^{2 '} each independently represents a hydrogen atom or a halogen 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, X ¹ to X ⁴ each independently represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group or a halogen atom; however, either Y ^{1 '} or Y ^{2 '} is a hydrogen atom, and the other is a ruthenium atom, when Y ^{1 '} or Y ^{2 '} is a hydrogen atom, R ¹ to R ³ or R ⁴ to R ⁶ are absent) (wherein, 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). The tetraphenylethane derivative according to claim 1, wherein one of Y ^{1 '} or Y ^{2 '} in the formula (1') is a hydrogen atom, and the other represents a halogen atom, Y ^{When 1'} or Y ^{2 '} is a halogen atom, R ¹ to R ³ or R ⁴ to R ⁶ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms.