TWI405785B - Liquid crystal sealant,liquid crystal display panel and fabricating method thereof using the same - Google Patents

Abstract

This invention provides a liquid crystal sealing agent which can be applied to liquid crystal display panels. The liquid crystal sealing agent comprises (a) a compound containing a (meth)acryloyl group and a glycidyl group in its molecule and having a number average molecular weight of 500 to 2000, (b) a heat latent curing agent, (c) a radical polymerization initiator, and (d) a filler. The component (a), despite its high molecular weight, has high reactivity and latent curability, and thus simultaneously has a low level of solubility in liquid crystals, a high level of curability, and a high level of viscosity stability. Accordingly, the manufacture of a liquid crystal display panel using the liquid crystal sealing agent is advantageous in that, while maintaining the high level of productivity, the strength of adhesion between a substrate and a cured product of the liquid crystal sealing agent is high and the contamination of the liquid crystal can be suppressed on a low level, resulting in the manufacture of liquid crystal display panels which can realize a high level of display and a high quality.

Description

Liquid crystal sealing agent, manufacturing method of liquid crystal display panel using the same, and liquid crystal display panel

The present application claims priority based on the application Nos. JP2006-243057, JP2006-243059, filed on Sep. 7, 2006, and the application No. JP2006-350198, JP2006-350137, filed on Dec. 26, 2006. The contents contained in these patent specifications are all used in this patent specification.

The present invention relates to a liquid crystal sealing agent, a method of manufacturing a liquid crystal display panel using the same, and a liquid crystal display panel.

In recent years, with the development of broadband, the development of small electronic devices such as digital cameras and mobile phones, the demand for liquid crystal displays as flat-panel displays has reached an unprecedented growth in terms of thinness, light weight, and low power consumption. The liquid crystal display panel has a structure in which liquid crystal is sealed between two substrates bonded together by a liquid crystal sealing agent, and a voltage is applied to the liquid crystal to control alignment of the liquid crystal, and modulation of light transmitted through the substrate is adjusted. The device to display the image.

Conventionally, a liquid crystal display panel is mainly produced by injecting liquid crystal into a liquid crystal cell having an injection port disposed between two substrates, and closing the injection port to produce a liquid crystal injection method of the liquid crystal display panel (for example, refer to the patent document) 1). However, with the increasing demand for liquid crystal display panels, there is a strong need to increase productivity in the field of manufacturing liquid crystal display panels. The current liquid crystal injection method takes time due to liquid crystal injection, and requires hardening of the liquid crystal sealing agent. Heating at a temperature of 120 to 150 ° C for several hours Reasons for its low productivity have become a major problem.

Therefore, recently, as a method of manufacturing a display panel instead of the liquid crystal injection method, a liquid crystal dropping method has been attracting attention. The liquid crystal dropping method refers to first forming a frame-like sealing pattern by a liquid crystal sealing agent on one of two substrates by using a dispenser or screen printing; and injecting a trace amount into the frame thus formed or another substrate. Liquid crystal; in a high vacuum, the two substrates are overlapped in a state in which the liquid crystal sealing agent is not hardened; after the liquid crystal sealing agent between the two substrates is irradiated with ultraviolet rays for a temporary hardening, the liquid crystal sealing agent is post-hardened by heating (after- Curing) A method of manufacturing a liquid crystal display panel.

According to the liquid crystal dropping method, the liquid crystal sealing agent is sealed for a short period of time, and the liquid crystal sealing agent is hardened by the combined use of light and heat pressing, thereby shortening the hardening time of the liquid crystal sealing agent, so that compared with the liquid crystal injection method, , productivity is improved. As a liquid crystal sealing agent used for the above-described liquid crystal dropping method, a liquid and a thermosetting liquid crystal sealing agent have been proposed (for example, refer to Patent Documents 2 and 3).

However, when the liquid crystal dropping method is used, since the liquid crystal directly contacts the liquid crystal sealing agent in an uncured state, the components of the liquid crystal sealing agent are eluted to the liquid crystal, and the liquid crystal is easily contaminated. If the liquid crystal is contaminated like this, the display property of the liquid crystal display panel is remarkably lowered, which is a major problem. Further, when an uncured portion is present in the cured product of the liquid crystal sealing agent, contamination of the liquid crystal is also caused. This is because the liquid crystal sealant component in an uncured state is eluted from the hardened portion to the liquid crystal. When the uncured portion remains in the cured product of the liquid crystal sealing agent, not only the liquid crystal is contaminated, but also the bonding strength between the substrate constituting the liquid crystal display panel and the cured product of the liquid crystal curing agent is lowered, resulting in a liquid crystal display panel. The possibility of quality degradation is high. Therefore, from the viewpoint of preventing liquid crystal contamination and high adhesion strength, it is desirable to provide a liquid crystal sealing agent which is high in curability and is excellent in solubility in liquid crystal, and is cured in various places in a short time to be cured. The unhardened portion is suppressed to a minimum.

Heretofore, as a liquid crystal sealing agent for improving the bonding strength, a liquid crystal containing a partially acrylated or partially methacrylized epoxy resin obtained by reacting a bisphenol A type epoxy resin with acrylic acid or methacrylic acid has been proposed. A sealant (for example, refer to Patent Document 4). Further, as a liquid crystal sealing agent capable of preventing liquid crystal contamination, an acrylonitrile-containing epoxy resin having a (meth)acrylic group and a hydroxyl group has been proposed, and the above (meth)acrylic group (( A liquid crystal sealing agent having a larger number of the above-mentioned hydroxyl groups than the above-mentioned hydroxyl group (for example, refer to Patent Document 5).

[Patent Document 1] International Publication No. 2004/039885

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-133794

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2002-214626

[Patent Document 4] Japanese Patent No. 3162179

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-195978

However, the partially acrylated epoxy resin described in Patent Document 4 has low curability and low molecular weight, so that solubility in liquid crystals is high, and liquid crystals are easily contaminated. Further, since the liquid crystal sealing agent is high in viscosity stability around room temperature, the viscosity stability is preferably high. The reason is that if the viscosity of the liquid crystal sealing agent is stable without changing around room temperature, the capacity is It is easy to form a seal pattern having a desired line width on the substrate, and it is possible to improve the yield at the time of manufacture of the liquid crystal display panel. On the other hand, since the above-mentioned partially methacrylated epoxy resin has low viscosity stability at room temperature, it is not preferable as a raw material of a liquid crystal sealing agent.

Further, the acrylated epoxy resin described in Patent Document 5 has high viscosity stability and is excellent, but on the other hand, since the curability is low, it is easy to leave an unhardened portion in the cured product of the liquid crystal sealing agent. Therefore, there is a problem that the contamination of the liquid crystal and the adhesion between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel are low.

Therefore, the present invention has the first object of providing a liquid crystal sealing agent which has high hardenability and low solubility to liquid crystal while maintaining high viscosity stability. Further, in order to prevent liquid crystal contamination by using the liquid crystal sealing agent of the present invention, and the liquid crystal display panel having high bonding strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel, high productivity can be maintained. The method of manufacturing is the second purpose.

As a result of the active research of the present inventors, it has been found that the above problems can be solved by using a compound which is polymerized within a predetermined range by focusing on the molecular weight of a compound used as a raw material of a liquid crystal sealing agent, and the present invention has been completed.

That is, the above problems are solved by the liquid crystal sealing agent of the present invention.

[1] A liquid crystal sealing agent comprising: (a) a compound having a (meth)acryloyl group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2000; (b) a heat potential a hardening agent; (c) a radical polymerization initiator; and (d) a filler.

[2] The liquid crystal sealing agent according to [1], wherein the component (a) is a compound represented by the following general formula (I).

In the above general formula (I): R ₁₁ to R ₁₆ each independently represent a hydrogen atom or a methyl group, but R ₁₃ and R _{14 are} not both methyl groups, and R ₁₅ and R _{16 are} not both. Methyl; X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the general formula (I-1); and one of X ₁₃ and X ₁₄ represents an alkylene group having 1 to 10 carbon atoms. a group represented by the general formula (I-2); A represents a group represented by the general formula (I-3a), (I-3b) or (I-3c); P independently represents a hydrogen atom, An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group; a, b, and c each independently represent an integer of 0 to 3, d represents an integer of 1 to 3, and m represents 0 to 4; An integer, where a+b+c+d+m=6, and a, b, and c are not 0 at the same time; j is an integer of 0 or 1, and k and 1 represent integers of 0-10.

In the above general formula (I-1): Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and Y ₂₁ is bonded to O of the above-mentioned general formula (I), and n represents An integer from 1 to 10.

In the above general formula (I-2): Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and Y ₃₂ is bonded to O of the above-mentioned general formula (I).

In the above general formula (I-3a): R ₄₁ and R ₄₂ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and Z is a single bond or a -O- group. , -S- group, -SO ₂ - group, -C(R ₄₃ )(R ₄₄ )- group, or a group represented by the following general formula (t1), wherein R ₄₃ and R ₄₄ are independently represented A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and r and s each independently represent an integer of 0 to 4.

In the above general formula (I-3b): R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group. .

In the above general formula (I-3c): R ₆₁ and R ₆₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[3] The liquid crystal sealing agent according to [1], wherein the general formula (I) is one or more of an acrylonitrile group, a methacryl fluorenyl group, and an epoxy group in a molecule. More than one compound.

[4] The liquid crystal sealing agent according to any one of [1] to [3] wherein the component (a) has an epoxidation having (i) 3 or 4 glycidyl groups in the molecule. A compound of (meth)acrylonyl group and glycidyl group obtained by reacting (ii) a (meth)acrylic acid derivative having a carboxyl group.

[5] The liquid crystal sealing agent according to [4], wherein the component (i) is a compound represented by the general formula (i-1), (i-2), (i-3) or (i-4) .

R ₇₁ in the above general formula (i-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ₇₁ in the above general formula (i-2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

【化10】

In the above general formula (i-4): R ₈₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₈₂ represents a hydrogen atom or a methyl group.

[6] The liquid crystal sealing agent according to [4], wherein the component (B) is a compound represented by acrylic acid, methacrylic acid, general formula (ii-1) or general formula (ii-2).

【化12】

In the above general formula (ii-1): R ₉₁ represents a hydrogen atom or a methyl group, X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (t2), and X ₄₂ represents a carbon number. 1 to 20 alkylene groups or 2 to 6 carbon atoms alkenylene.

In the above general formula (t2): Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ₅₁ represents an acrylonitrile group in the above general formula (ii-1), and n represents 1 to 10 Integer.

In the above general formula (ii-2): R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group, X ₆₁ represents a group represented by the following general formula (t3), and X ₆₂ represents a subunit having a carbon number of 1 to 10. The alkyl group, X ₆₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and i and j each independently represent an integer of 0 or 1.

In the above general formula (t3): Y ₇₁ and Y ₇₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and the CO group is bonded to O of the above-mentioned general formula (ii-2).

[7] The liquid crystal sealing agent according to any one of [1] to [6], further comprising any one of (e) an epoxy resin or (f) an acrylic compound.

The liquid crystal sealing agent of any one of [1], wherein the component (c) is a photoradical polymerization initiator.

The liquid crystal sealing agent of any one of [1], wherein the component (c) is a thermal radical polymerization initiator.

[10] The liquid crystal sealing agent according to any one of [1] to [9], wherein the component (a) is added in an amount of 5 to 90 parts by mass based on 100 parts by mass of the liquid crystal sealing agent.

Further, the above problems are also solved by the method of manufacturing a liquid crystal display panel of the present invention and the liquid crystal display panel obtained by the method.

[11] A method of manufacturing a liquid crystal display panel, wherein a liquid crystal display panel is manufactured by laminating two opposing substrates by a liquid crystal sealing agent, and the method includes: preparing a process of preparing one or more substrates, wherein the substrate has a substrate a frame-shaped display region formed by the liquid crystal sealing agent according to any one of the above [1] to [10]; the liquid crystal is instilled into the display region in an uncured state or on another substrate a process of superposing the substrate in which the liquid crystal is dropped and another substrate; and a process of irradiating light and heating the liquid crystal sealing agent sandwiched between the two substrates, or performing only one of irradiation light and heating .

[12] A liquid crystal display panel obtained by the method for producing a liquid crystal display panel according to [11] above.

According to the present invention, it is possible to provide a liquid crystal sealing agent which has high adhesion strength between a cured product of a liquid crystal sealing agent and a substrate constituting a liquid crystal display panel, and which can prevent liquid crystal contamination, in addition to high viscosity stability and high hardenability. Moreover, by using the liquid crystal sealing agent of the present invention, it is possible to provide a method of manufacturing a liquid crystal display panel which can obtain a high quality liquid crystal display panel while maintaining high productivity.

Next, the present invention will be described in detail. The liquid crystal sealing agent of the present invention is characterized by comprising: (a) a compound having a (meth)acrylonyl group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2,000; (b) a thermal latent curing agent; c) a radical polymerization initiator; and (d) a filler. The respective components of the liquid crystal sealing agent used in the present invention will be described below.

[(a) a compound having a (meth)acryloyl group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2,000]

(a) A compound having a (meth) acrylonitrile group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2,000 (also referred to as "(a) component") means that propylene is contained in the molecule. A compound having a methacryloyl group and a glycidyl group and having a number average molecular weight of from 500 to 2,000. The above number average molecular weight can be measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard.

As described above, since the component (a) of the present invention includes a (meth)acryl fluorenyl group indicating potential hardenability, the viscosity stability is high even in a low temperature region such as near room temperature. On the other hand, when the component (a) is used as a raw material of the liquid crystal sealing agent, a liquid crystal sealing agent having high curability is obtained. Such a liquid crystal sealing agent has high storage stability and high coatability to a substrate, and is hardened to various corners in a short time even in a place such as a light-shielding region. As a result, it is possible to prevent the contamination of the liquid crystal, and the bonding strength between the cured product of the liquid crystal sealing agent and the substrate is high, and the liquid crystal display panel having good display properties can be manufactured while maintaining high productivity.

Further, the number average molecular weight of the component (a) of the present invention is adjusted in the range of 500 to 2,000. Therefore, there is a feature that the solubility of the liquid crystal is suppressed to be low. In general, the viscosity of a compound which is highly polymerized tends to be high. However, when the number average molecular weight is adjusted within the above range, a liquid crystal sealant having a low viscosity can be obtained while suppressing liquid crystal contamination. In addition, from the viewpoint of reducing the solubility to liquid crystals and making them low in viscosity It should be noted that the number average molecular weight of the component (a) is preferably 800 to 1800.

The first component (a) is preferably one or more of an acryloyl group, a methacryl fluorenyl group, and an epoxy group in the molecule, from the viewpoint of improving both the curability of the liquid crystal sealing agent and the decrease in liquid crystal contamination. More than one compound. The more the content of the epoxy group or the like having high reactivity, the more the curability of the compound is improved. Further, the more the compound of the component (a) is polymerized, the more the liquid crystal contamination can be prevented.

When the component (a) is used as a raw material of the liquid crystal sealing agent, the amount of the component (a) used is preferably from 5 to 90 parts by mass, more preferably from 20 to 60 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. Therefore, the characteristics of the component (a) are preferably reflected as characteristics of the liquid crystal sealing agent, and the bonding strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel is high, and the display can be obtained. Excellent liquid crystal display panel.

[First (a) component]

The component (a) of the present invention is preferably a compound represented by the following general formula (I) (also referred to as "first (a) component)".

In the above general formula (I): R ₁₁ to R ₁₆ each independently represent a hydrogen atom or a methyl group, but R ₁₃ to R _{14 are} not both methyl groups, and R ₁₅ to R _{16 are} not both. Methyl; X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the general formula (I-1); and one of X ₁₃ and X ₁₄ represents an alkylene group having 1 to 10 carbon atoms. a group represented by the general formula (I-2); A represents a group represented by the general formula (I-3a), (I-3b) or (I-3c); P independently represents a hydrogen atom, An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a nitro group; a, b, and c represent an integer of 0 to 3, d represents an integer of 1 to 3, and m represents an integer of 0 to 4; Here, a+b+c+d+m=6, and a, b, and c are not 0 at the same time; j is an integer of 0 or 1, and k and 1 represent integers of 0-10.

In the above general formula (I-1): Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and Y ₂₁ is bonded to O of the above-mentioned general formula (I), and n represents An integer from 1 to 10.

In the above general formula (I-2): Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and Y ₃₂ is bonded to O of the above-mentioned general formula (I).

In the above general formula (I-3a): R ₄₁ and R ₄₂ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and Z is a single bond or a -O- group. , -S- group, -SO ₂ - group, -C(R ₄₃ )(R ₄₄ )- group, or a group represented by the following general formula (t1), wherein R ₄₃ and R ₄₄ are independently represented A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and r and s each independently represent an integer of 0 to 4.

In the above general formula (I-3b): R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group. .

In the above general formula (I-3c): R ₆₁ and R ₆₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The compound of the formula (I) can be reacted by reacting (i) benzenedicarboxylic acid anhydride or benzene tetracarboxylic anhydride with (ii) hydroxyl group-containing (meth) acrylate. A carboxylate ester group and a carboxyl group are formed, and (iii) a carboxyl group formed by the above reaction is bonded to a polyglycidyl ether to be synthesized.

Examples of the above (i) phthalic anhydride, pyromellitic dianhydride or benzene tricarboxylic anhydride include: phthalic anhydride, Dodecenyl phthalic anhydride ), Octenyl phthalic anhydride, 1,2,4,5-pyromellitic dianhydride. These compounds may be used singly or in combination of plural kinds.

Examples of the above (ii) hydroxyl group-containing (meth) acrylate include: hydroxyalkyl (meta) acrylate, polyalkylene glycol (carbon) 2~6) monoalkyl (meth) acrylate (polyalkylene (carbon number 2 ~ 6) glycol mono (meta) acrylate, glycerol mono (meth) acrylate (glycerol Mono(meta)acrylate), glycerol diacrylate, glycerol acrylate metaacrylate, pentaerythritol tri(meth)acrylate, cyclohexanedimethanol mono(methyl) Cyclohexanedimethanol mono(meta)acrylate, or a modified ester of these lactones (carbon number 4-8) or an alkylene oxide (carbon number 2-6) modified compound. These compounds may be used singly or in combination of plural kinds.

Examples of the above (iii) polyglycidyl ether include: phenol novolac type glycidyl ether, biphenyl novolac type glycidyl ether, cresol novolac type glycidyl ether, bisphenol A type glycidyl ether , bisphenol AD glycidyl ether, bisphenol F glycidyl ether, diphenyl ether type glycidyl ether, sulfide type glycidyl ether, oxysulfide type shrinkage Glycerol ether, fluorene type glycidyl ether, adamantyl type glycidyl ether, resorcin type glycidyl ether, catechol type glycidyl ether, hydrogen Hydroquinone type glycidyl ether. These compounds may be used singly or in combination of plural kinds.

The compound represented by the above general formula (I) must include an acrylonitrile group or a methacryl group, and a glycidyl group in the molecule.

For the reaction between benzenedicarboxylic acid anhydride or benzene tetracarboxylic anhydride and hydroxyl group-containing (meth) acrylate, the reaction of bonding polyglycidyl ether is promoted From the viewpoint of the reaction, it is preferred to keep the reaction temperature substantially constant within the range of 40 to 180 ° C, and more preferably 50 to 130 ° C. The above reaction temperature means a temperature in a reaction mixture obtained by mixing various raw materials of the first component (a). The temperature of the reaction mixture can be easily measured using a thermometer or the like.

In the reaction of bonding a glycidyl ether, it is preferred to use a catalyst from the viewpoint of promoting the reaction. Preferable examples of the catalyst used herein include: an organic phosphine compound, a tertiary amine compound, a fourth-order ammonium salt compound, an organic phosphate compound, an imidazole compound, and an organic compound. Metal compound.

Examples of the above organic phosphine compound include triphenylphosphine. Examples of the above tertiary amine compound include triethylamine and triethanolamine. Examples of the above-mentioned fourth-order ammonium salt compound include trimethyl ammonium chloride, and triethyl benzyl ammonium chloride. The above organic phosphate compound includes tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. Examples of the above imidazole compound include 2-methylimidazole. Examples of the above organometallic compound include cobalt octenate.

The amount of the above catalyst to be used is preferably an amount which can sufficiently promote the reaction. Specifically, the amount of the catalyst used is preferably from 0.01 to 5.0% by mass based on the total mass of the reaction mixture.

A polymerization inhibiting agent may also be added to the above reaction mixture as needed. The polymerization inhibiting agent refers to a compound for suppressing or stopping the progress of the polymerization reaction in the reaction mixture. However, it is not particularly limited to a polymerization inhibitor, and may be appropriately selected. The known compound can be used. Preferable examples of the polymerization inhibiting agent include: hydroquinone, methylhydroquinone, hydroxymonomethylether, phenothiazine, pt-butylcatechol (pt-butylcatechol). ), p-benzoquinone, naphthoquinone. These compounds may be used singly or in combination of plural kinds.

Additionally, an organic solvent can be added to the reaction mixture. Examples of the organic solvent include an aromatic solvent such as toluene or xylene; a ketone solvent such as cyclohexanone; and a glycerin solvent such as propylene glycol monomethyl ether, but are not particularly limited. . These organic solvents may be used singly or in combination of plural kinds.

[Second (a) component]

In a preferred embodiment of the component (a) of the present invention, in addition to the above first component (a), an epoxy compound having (i) having 3 or 4 glycidyl groups in the molecule and (ii) having a carboxyl group are included. A (meth) acrylonitrile group and a glycidyl group compound (also referred to as a second (a) component) obtained by reacting a (meth)acrylic acid derivative.

The method for producing the second component (a) of the present invention is not particularly limited, and for example, a glycidyl group of one or two of the glycidyl groups in the component (i) may be reacted with a carboxyl group in the component (ii). Methods.

The component (i) used as a raw material of the second component (a) is not particularly limited as long as it has 3 or 4 glycidyl groups in the molecule, but is preferably used as a raw material of a liquid crystal sealing agent. The component (a) and the component (i) preferably have a molecular weight of 400 to 800. As having the above points Preferable examples of the component (i) include the compounds represented by the following general formula (i-1), (i-2), (i-3) or (i-4).

R ₇₁ in the above general formula (i-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ₇₁ in the above general formula (i-2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the above general formula (i-4): R ₈₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₈₂ represents a hydrogen atom or a methyl group.

Examples of the above-mentioned R ₇₁ and the alkyl group having 1 to 10 carbon atoms represented by the above R ₈₁ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and an s-butyl group. T-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, anthryl and fluorenyl. Among them, a hydrogen atom, a methyl group and an ethyl group are preferred, and a hydrogen atom is more preferred.

The trifunctional epoxy compound represented by the above general formula (i-1) and the tetrafunctional epoxy compound represented by the above general formula (i-2) may be commercially available or synthetic. In the synthesis of the above epoxy compound, the synthesis method is not particularly limited. When synthesizing these compounds, for example, a trinuclear or tetranuclear compound of a novolac type compound obtained by a condensation reaction between a phenol derivative and formalin, the epihalohydrin is reacted in accordance with a known epoxidation reaction. For synthesis. Further, in the above-described examples of the known epoxidation reaction, a method known as an industrial production method of a conventional epoxy compound which can be obtained as an industrial raw material is known.

Further, the compound represented by the above general formula (i-3) and general formula (i-4) is not particularly limited, and may be a commercially available product or a synthetic product.

The component (ii) of the present invention has a viewpoint of high reactivity of the liquid crystal sealing agent and high viscosity stability from the viewpoint of high molecular weight of the component (a) and a material of the liquid crystal sealing agent (a). In other words, it is preferably a compound represented by the following formula (ii-1) or general formula (ii-2) of acrylic acid, methacrylic acid.

In the above general formula (ii-1): R ₉₁ represents a hydrogen atom or a methyl group, X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (t2), and X ₄₂ represents a carbon number. 1 to 20 alkylene groups or 2 to 6 carbon atoms alkenylene.

Preferred examples of the alkylene group having 1 to 10 carbon atoms as X ₄₁ in the above general formula (ii-1) include a methylene group, an ethylene group, a methylethylene group, and a trimethylene group. Tetramethylene, pentamethylene, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene ( Octamethylene group), nonamethylene group, decamethylene group. Among them, X _{41 is} preferably an alkylene group having 2 to 6 carbon atoms or a group represented by the following general formula (t2).

Preferred examples of the alkylene group having 1 to 20 carbon atoms as X ₄₂ in the above general formula (ii-1) include a methylene group, an ethylene group, a methylethylene group, and a trimethylene group. Tetramethylene, pentamethylene, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene ( Octamethylene group), nonamethylene group, decamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group And octade methylene (octadecamethylene group).

Preferred examples of the alkenylene having 2 to 6 carbon atoms as X ₄₁ in the above general formula (ii-1) include: -CH=CH- group, -CH=CH-CH ₂ - group, -CH =CH-CH ₂ -CH ₂ - group, -CH ₂ -CH=CH-CH ₂ - group. Wherein, as X ₄₂ , an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group; and -CH=CH are preferred. The group is more preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and a -CH=CH- group.

In the above general formula (t2): Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and Y ₅₁ is bonded to O of the above-mentioned general formula (ii-1), and n represents An integer from 1 to 10.

Preferred examples of the alkylene group having 1 to 10 carbon atoms as Y ₅₁ and Y ₅₂ in the above general formula (t2) include a methylene group, an ethylene group, a methylethylene group, and a trimethylene group. , tetramethylene, pentamethylene, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethyl (octamethylene group), nonamethylene group, decamethylene group. Among them, it is preferably an alkylene group having 2 to 6 carbon atoms. Further, n in the above general formula (t2) represents an integer of 1 to 10, but is preferably an integer of 1 to 6.

In the above general formula (ii-2): R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group, X ₆₁ represents a group represented by the following general formula (t3), and X ₆₂ represents a subunit having a carbon number of 1 to 10. The alkyl group, X ₆₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms.

i and j each independently represent an integer of 0 or 1.

In the above general formula (t3): Y ₇₁ and Y ₇₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and the CO group is bonded to O of the above-mentioned general formula (ii-2).

Preferred examples of the alkylene group having 1 to 10 carbon atoms as R ₆₁ and R ₆₂ in the above general formula (ii-2) include methylene, ethylene, methylethylene group, and Sanya. Methyl, tetramethylene, pentamethylene, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, VIII An octamethylene group, a nonamethylene group, and a decamethylene group.

Preferred examples of the alkylene group having 1 to 20 carbon atoms as X ₆₃ in the above general formula (ii-1) include a methylene group, an ethylene group, a methylethylene group, and a trimethylene group. Tetramethylene, pentamethylene, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene ( Octamethylene group), nonamethylene group, decamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group And octade methylene (octadecamethylene group).

Preferred examples of the alkenylene having 2 to 6 carbon atoms as X ₆₃ in the above general formula (ii-2) include: -CH=CH- group, -CH=CH-CH ₂ - group, -CH =CH-CH ₂ -CH ₂ - group and -CH ₂ -CH=CH-CH ₂ - group. Among them, as X ₅₃ , an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group is preferable, and -CH=CH The group is more preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and a -CH=CH- group.

Y ₇₁ and Y ₇₂ in the above general formula (t3) should be as described above for X ₆₁ . Preferred examples of the alkylene group as Y ₇₁ and Y ₇₂ 0 include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a ring arylene group. Cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, Decamethylene group. Among them, the alkylene group is preferably an alkylene group having 2 to 6 carbon atoms.

[Method for Producing Compound of General Formula (ii-1)]

The compound represented by the above formula (ii-2) can be industrially produced, or can be easily "having a hydroxyl group-containing (meth)acrylic acid derivative" and "having two" represented by the following Reaction Formulas 1 to 3. It is produced by an esterification reaction between a compound of a carboxyl group. Here, the above-mentioned examples of the carboxyl group may also include, for example, antimony halide A precursor of a carboxyl group of an acid group or an acid anhydride group.

[Reaction formula 1]

The reaction of the following Reaction Scheme 1 is a partial esterification reaction between a compound having two carboxyl groups represented by the general formula (ii-1a) and a compound having a hydroxyl group represented by the general formula (ii-1b). The partial esterification reaction refers to a reaction of esterifying a part of a carboxyl group of a compound having a plurality of carboxyl groups in a molecule using a compound having a hydroxyl group.

In the above Reaction Formula 1: X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or the above general formula ( The group shown by t2), R ₉₁ represents a hydrogen atom or a methyl group.

In the reaction of the reaction formula 1, the amount ratio between the compound represented by the above formula (ii-1a) and the compound represented by the above formula (ii-1b) is not particularly limited, but it is necessary as a final target. That is, a carboxyl group is left in the compound of the general formula (ii-1), so that the amount of the hydroxyl group used is preferably less than the total amount of the carboxyl group. Specifically, when the mass of the compound represented by the above formula (ii-1a) is M1 and the mass of the compound represented by the above formula (ii-1b) is M2, it is preferably M1/M2=1.

In the reaction of the reaction formula 1, when the amount of the hydroxyl group used is more than the total amount of the carboxyl group, the esterification reaction is excessively promoted in the reaction mixture of the reaction formula 1, and it is difficult to partially retain the carboxyl group in the final target. In this case, it is necessary to stop the esterification reaction in the course of the reaction to leave a carboxyl group in the final target, but it is not easy to stop it at the stage of the desired reaction rate, so the amount of each organic group should be appropriately adjusted. .

The above reaction rate can be grasped by a known analysis means. Preferable examples of the means for analyzing the reaction rate include a liquid chromatograph, a thin layer chromatography, and an IR analyzer. Further, in the above Reaction Formula 1, in order to produce a compound represented by the general formula (ii-1), which is a final target, more reliably and with a higher purification yield, it is preferred to carry out the esterification reaction while measuring the reaction rate as appropriate.

In the partial esterification reaction of Reaction Formula 1, an esterification catalyst can also be used from the viewpoint of promoting the reaction. The esterification catalyst refers to a catalyst that activates the esterification reaction between a carboxylic acid and an alcohol. Preferable examples of the esterification catalyst include mineral acid, organic acid, and Lewis acid, but are not particularly limited, and a compound known as an esterification catalyst may be used. Examples of the above mineral acid include hydrochloric acid or sulfuric acid. Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Further, examples of the above Lewis acid include boron trifluoride and aluminum trichloride.

The amount of the above esterification catalyst to be used is preferably an amount which can sufficiently promote the above partial esterification reaction. From the viewpoint of promoting the partial esterification reaction, the esterification catalyst is preferably used in an amount of from 0.001 to 50% by mass, more preferably from 0.01 to 30% by mass, based on the total mass of the reaction mixture.

Further, in the above partial esterification reaction, water is generated during the reaction. this In order to promote the above reaction, water of by-products is preferably removed from the reaction mixture. The method for removing water from the reaction mixture is not particularly limited, and includes, for example, a method in which a solvent having a boiling point substantially the same as that of benzene or toluene, a method in which the solvent is azeotroped with water, or a method in which a dehydrating agent such as a molecular sieve is used.

The reaction of the reaction formula 1 can also be carried out in a solvent-free or solvent inert to the reaction. Examples of the solvent to be preferably used in the reaction formula 1 include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, and a halogen solvent, but are not particularly limited.

Examples of the above hydrocarbon solvent include n-hexane, benzene or toluene. Examples of the above ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the above ester solvent include ethyl acetate or butyl acetate. Examples of the above ether solvent include diethyl ether, tetrahydrofuran or dioxane. Further, examples of the above halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Perclene (general name of tetrachloroethylene). These solvents may be used singly or in combination of plural kinds.

The reaction temperature of the reaction formula 1 is not particularly limited, but is preferably kept constant in the range of 50 to 150 ° C from the viewpoint of high short-term efficiency and sufficient promotion of the partial esterification reaction, and is 70-120. °C is even better.

The reaction time of the reaction formula 1 is appropriately determined depending on the reaction temperature, the compound represented by the above formula (ii-1a), the compound represented by the above formula (ii-1b), the type, combination, and amount of the reaction solvent. The setting is not particularly limited. In view of the degree of progress of the above partial esterification reaction, etc., it is preferably in the range of several minutes to 100 hours, more preferably 0.5 to 50 hours, particularly preferably 1 to 20 hours.

[Reaction formula 2]

As shown below, the reaction of the reaction formula 2 is a partial esterification between a compound having two halogenated fluorenyl groups represented by the general formula (ii-1c) and a compound having a hydroxyl group represented by the general formula (ii-1b). The reaction, and a two-stage reaction of a compound of the general formula (ii-1) which hydrolyzes the remaining halogenated sulfhydryl group in the reaction mixture to form a final target.

In the above Reaction Scheme 2: X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the above general formula (t2), and X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or a carbon number of 2 to 6 Alkenylene, R ₉₁ represents a hydrogen atom or a methyl group, and COL represents a halogenated fluorenyl group, wherein L represents a halogen (Cl or Br).

In Reaction Scheme 2, a carboxyl group must be left in the final target. Therefore, in the above partial esterification reaction as the first-stage reaction of the reaction formula 2, it is preferred to make the amount of the hydroxyl group less than the total amount of the halogenated fluorenyl group. Here, if the amount of the hydroxyl group is made larger than the total amount of the halogenated fluorenyl group, it is necessary to stop the reaction at the stage of the desired reaction rate. However, this is not desirable because it is difficult to stop the reaction accurately at the desired reaction rate.

The above reaction rate can be measured by a known analytical means. When the reaction rate is appropriately measured during the execution of the reaction formula 2, the reaction can be stopped or carried out at the stage of the desired reaction rate. Examples of such analytical means include liquid chromatography, thin layer chromatography or IR analysis devices.

The above partial esterification reaction can also be carried out in a solvent-free or solvent inert to such a reaction. Examples of the solvent include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, and a halogen solvent.

Examples of the above hydrocarbon solvent include n-hexane, benzene or toluene. Examples of the above ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the above ester solvent include ethyl acetate or butyl acetate. Examples of the above ether solvent include diethyl ether, tetrahydrofuran or dioxane. Further, examples of the above halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Perclene (general name of tetrachloroethylene). These solvents may be used singly or in combination of plural kinds.

In the above partial esterification reaction, a hydrogen halide (e.g., hydrogen chloride or the like) as a by-product is formed by the reaction of a halogenated fluorenyl group with a hydroxyl group. Since the above hydrogen halide has a possibility of lowering the characteristics of the reaction product, it is preferred to remove it from the reaction mixture as much as possible. The method for removing the hydrogen halide is not particularly limited, and a known method can be used. However, from the viewpoint of easy handling, a dehydrolalogenation agent is useful.

Preferable examples of the dehydrolalogenation agent include an organic base compound or an inorganic base compound. Examples of the above organic base compound include: triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8- Diazabicyclo [5.4.0] Eleven-7-ene (DBU). Further, examples of the inorganic base compound include sodium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and sodium oxide. These compounds may be used singly or in combination of plural kinds.

The amount of the above dehydrohalogenating agent to be used is not particularly limited, and it is preferred to sufficiently remove the amount of hydrogen halide formed in the reaction mixture. From this point of view, the amount of the dehydrohalogenating agent to be used is preferably from 0.1 to 10 moles, more preferably from 0.5 to 5 moles, particularly preferably from 1 to 3 moles, per mole of the hydroxyl group.

In Reaction Scheme 2, the hydrolysis reaction as the second-stage reaction is carried out by adding water to the reaction mixture obtained at the end of the partial esterification reaction in the first stage. The method of adding water to the reaction mixture after completion of the partial esterification reaction is not particularly limited, and may be added all at once, or water may be added by dripping. Among them, the latter which is carried out by the dropping method is preferable from the viewpoint of allowing the reaction to proceed slowly.

From the viewpoint of promoting the hydrolysis reaction, the amount of water used in the hydrolysis reaction is preferably from 1 to 100 moles, more preferably from 5 to 50 moles, relative to the 1 mole of halogenated sulfonium group remaining in the reaction mixture. .

The above hydrolysis reaction can confirm the reaction rate in the reaction mixture by a known analysis means when water is dripped, and continue or stop the dripping of water at a desired reaction rate, thereby causing the reaction to proceed or stop. Examples of the means of analysis include a liquid chromatograph, a thin layer chromatography, and an IR analysis device.

Further, in the above hydrolysis reaction, a hydrogen halide (e.g., hydrogen chloride or the like) as a by-product is formed by the reaction of the residual acid halide with the added water, but the hydrogen halide may cause a decrease in the characteristics of the reaction product. Therefore, The hydrogen halide formed in the reaction mixture is removed as much as possible. The method of removing the hydrogen halide is not particularly limited, and from the viewpoints of workability and availability, it is preferred to use a dehydrologenogenation agent.

Examples of the above dehydrolalogenation agent include an organic base compound or an inorganic base compound. Specifically, examples of the above organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU). On the other hand, examples of the above inorganic base compound include sodium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and sodium oxide. These compounds may be used singly or in combination of plural kinds.

The amount of the above dehydrohalogenating agent to be used is not particularly limited, and it is preferably such that the amount of hydrogen halide present in the reaction mixture can be sufficiently removed. From this point of view, the amount of the dehydrohalogenating agent to be used is preferably from 0.5 to 10 moles, more preferably from 1 to 5 moles, per mole of the halogenated sulfhydryl group.

In the reaction formula 2, the reaction temperature of the partial esterification reaction and the water addition reaction is not particularly limited, but from the viewpoint of promoting the partial esterification reaction, it is preferably kept constant in the range of -78 to 150 °C. It is better at -20~100°C, especially at 0~80°C.

The reaction time of the above partial esterification reaction is appropriately set depending on the reaction temperature, the kind of the solvent to be used, and a combination thereof, and the compound represented by the above general formula (ii-1b) and the compound represented by the above general formula (ii-1c). The amount of use or the like is not particularly limited. From the viewpoint of promoting the above reaction, it is generally preferably from several minutes to 100 hours, more preferably from 30 minutes to 50 hours. at this time, When the reaction time is from 1 to 20 hours, the above reaction can be promoted without lowering the productivity, which is particularly preferable.

[Reaction formula 3]

As shown below, the reaction of the following Reaction Formula 3 is a ring-opening esterification between a compound having an acid anhydride group represented by the general formula (ii-1e) and a compound having a hydroxyl group represented by the general formula (ii-1b). reaction. The reaction of the reaction formula 3 can easily obtain the compound represented by the above general formula (ii-1) in which a carboxyl group is retained by a ring-opening esterification reaction. Therefore, in the reaction formulae 1-3, the method of producing the compound represented by the above general formula (ii-1) is most preferable.

In the above Reaction Formula 3: X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the above general formula (t2), and X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or a carbon number of 2 to 6 Alkenylene, R ₉₁ represents a hydrogen atom or a methyl group.

In the above-mentioned ring-opening esterification reaction, the mixing ratio of the acid anhydride group and the hydroxyl group is not particularly limited, but from the viewpoint of promoting the above-described ring-opening esterification reaction, the amount of the hydroxyl group used is preferably 1 mol with respect to the acid anhydride group. 0.1 to 10 m, more Good for 0.5~5 moles, especially 0.8~3 moles.

The above ring-opening esterification reaction can also be carried out in a solvent-free or solvent inert to the reaction. Examples of the solvent include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, a halogen solvent, and a polar solvent, but are not particularly limited.

Examples of the above hydrocarbon-based solvent include n-hexane, benzene, toluene or xylene. Examples of the above ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the above ester solvent include ethyl acetate or butyl acetate. Examples of the above ether solvent include diethyl ether, tetrahydrofuran or dioxane. Examples of the above halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Perclene (general name of tetrachloroethylene). Further, examples of the above polar solvent include: N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, Dimethyl sulfoxide and cyclobutyl hydrazine. These solvents may be used singly or in combination of plural kinds.

The catalyst for the activation reaction may also be used in the above-mentioned ring-opening esterification reaction. Examples of such a catalyst include an organic phosphine compound, a tertiary amine compound, a fourth-order ammonium salt compound, an organic phosphate compound, an imidazole compound, and an organometallic compound.

Examples of the above organic phosphine compound include triphenylphosphine. Examples of the above tertiary amine compound include triethylamine and triethanolamine. Examples of the above-mentioned fourth-order ammonium salt compound include trimethyl ammonium chloride, triethylbenzylammonium chloride. (triethyl benzyl ammonium chloride). The above organic phosphate compound includes tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. Examples of the above imidazole compound include 2-methylimidazole. Examples of the above organometallic compound include cobalt octenate. These compounds may be used singly or in combination of plural kinds.

The amount of the above catalyst to be used is preferably in the range of 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, based on the mass of the reaction mixture, from the viewpoint of obtaining a sufficient reaction rate at the time of the reaction.

The reaction temperature of the above-mentioned ring-opening esterification reaction is not particularly limited, but is preferably kept constant in the range of 0 to 200 ° C from the viewpoint of efficiently and efficiently performing the above reaction, and is 0 to 150 ° C. better.

The reaction time of the above-mentioned ring-opening esterification reaction depends on the reaction temperature, the amount of the compound represented by the above formula (ii-1b), the compound represented by the above general formula (ii-1e), or the kind and combination of the reaction solvent. It is not particularly limited as long as it is appropriately set. From the viewpoint of efficiently and efficiently performing the above reaction, it is preferably from several minutes to several tens of hours.

Further, in Reaction Formula 3, the reaction rate may be confirmed by a known analysis means, and the reaction may be carried out at an arbitrary reaction rate or the reaction may be stopped. Examples of the above analysis means include a liquid chromatograph, a thin layer chromatography apparatus, and an IR analysis apparatus.

[Compound of general formula (ii-2)]

Next, the compound represented by the above general formula (ii-2) will be described. Above general The compound represented by the formula (ii-2) is obtained by substituting the compound represented by the general formula (ii-1b) used in the above reaction formulas 1 to 3 with a hydroxyl group as shown in the following general formula (ii-2a). It is made of a (meth)acrylic acid derivative.

In the above general formula (ii-2a): R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group, X ₆₁ represents a group represented by the above general formula (t3), and X ₆₂ represents an alkylene group having a carbon number of 1 to 10. Bases, i and j, respectively, represent integers of 0 or 1.

[Reaction formula 4]

The compound represented by the above general formula (ii-2a) is produced based on the following Reaction Formula 4.

In Reaction Scheme 4: R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group, X ₆₁ represents a group represented by the above general formula (t3), and X ₆₂ represents an alkylene group having 1 to 10 carbon atoms, i and j. An integer representing 0 or 1 is independently represented.

The reaction of the above Reaction Formula 4 is a ring-opening ester between a compound having a glycidyl ether group represented by the above general formula (ii-2a) and a compound having an alcohol group represented by the above general formula (ii-2c) The reaction is carried out to synthesize the reaction of the (meth)acrylic acid derivative having a hydroxyl group represented by the general formula (ii-2a).

The ring-opening esterification reaction of Reaction Scheme 4 can also be carried out in a solvent-free or solvent inert to such a reaction. Examples of such a solvent include a hydrocarbon solvent such as n-hexane, benzene, toluene or xylene; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; diethyl ether, tetrahydrofuran or dioxane; Ether solvent; halogenated solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Perclene (general name of tetrachloroethylene); N,N-dimethylformamide a polar solvent such as N,N-dimethylacetamide, dimethylimidazolidinone, dimethyl hydrazine or cyclobutyl hydrazine. These solvents may be used singly or in combination of plural kinds.

In the above-described ring-opening esterification reaction, a catalyst which functions in an activation reaction may also be used as needed. Examples of such a catalyst include: an organic phosphine compound such as triphenylphosphine; a tertiary amine such as triethylamine or triethanolamine; and trimethyl ammonium chloride. a fourth-order ammonium salt compound such as triethyl benzyl ammonium chloride; tetrabutylphosphonium bromide, bromination An organometallic compound such as an organic phosphate such as tetraphenylphosphonium bromide; an imidazole such as 2-methylimidazole or a cobalt octenate; or the like. These catalysts can be used alone or in combination.

The catalyst is preferably used in an amount of from 0.01 to 10.0% by mass, more preferably from 0.01 to 5.0% by mass, based on the total mass of the reaction mixture of the reaction formula 4 from the viewpoint of obtaining a sufficient reaction rate at the time of the reaction. In the present invention, in the case where a plurality of activating catalysts are used, the total amount of use of these catalysts is regarded as the amount of use of the catalyst.

The reaction temperature of the above-mentioned ring-opening esterification reaction is not particularly limited as long as it is a temperature required for carrying out the reaction. The above reaction temperature is preferably kept constant in the range of 0 to 200 ° C, more preferably 0 to 150 ° C.

The reaction time of the above-mentioned ring-opening esterification reaction is based on the reaction temperature, the compound represented by the above formula (ii-2b) used as a raw material, the compound represented by the above general formula (ii-2c), or the solvent. It is not particularly limited as long as it is appropriately set in accordance with the type and combination of the catalyst, the amount of use, and the like. From the viewpoint of sufficiently carrying out the above reaction, it is usually from several minutes to several tens of hours.

Further, in Reaction Formula 4, the reaction rate may be confirmed by a known analysis means, and the reaction may be carried out at an arbitrary reaction rate or the reaction may be stopped. Examples of the means of analysis include a liquid chromatograph, a thin layer chromatography, and an IR analysis device.

[Reaction formula 5]

The preferred second component (a) of the present invention can be, for example, given by the following reaction formula 5 The reaction shown is obtained.

In Reaction Scheme 5: X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or the above general formula (t2) The group shown, R ₇₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₉₁ represents a hydrogen atom or a methyl group.

The reaction of the above Reaction Formula 5 is a compound having three glycidyl groups represented by the above general formula (i-1) and a compound having a carboxyl group represented by the above general formula (ii-1) as a raw material, by continuously Performing a ring-opening esterification reaction to finally produce a reaction of a compound represented by the general formula (iii-2) having a glycidyl group and a (meth)acryloyl group in the molecule ("also referred to as Continuous ring-opening esterification reaction").

In the above continuous ring-opening esterification reaction, first, the compound represented by the above general formula (i-1) is used as a starting material, and the compound has a glycidyl group and the above general formula (ii-1) The carboxyl group in the compound shown is subjected to a ring-opening esterification reaction to form a compound of the general formula (iii-1) which is a difunctional epoxy resin. Then, the compound represented by the general formula (iii-1) is further subjected to a ring-opening esterification reaction with a compound represented by the general formula (ii-1) to finally form a compound represented by the general formula (iii-2).

The compound represented by the above general formula (iii-2) is an ideal high molecular weight which suppresses the solubility of the liquid crystal to be low. Further, since it has a glycidyl group in the molecule and has high reactivity with an epoxy curing agent, it exhibits high hardenability even in a place such as a light-shielding region.

In the above continuous ring-opening esterification reaction, the mixing ratio of the glycidyl group to the carboxyl group is not particularly limited, but in the reaction formula 5, it must be used as a reaction route. The compound of the above general formula (iii-1), and the glycidyl group of the above general formula (iii-2) as a final target are left in the product. Therefore, the carboxyl group is preferably used in an amount less than the amount of glycidyl group used. Specifically, the compound represented by the above formula (ii-1) is preferably used in an amount of from 1 to 2.8 mol, more preferably 1.3, based on the compound 1 mol represented by the above formula (i-1). ~2.5 m.

In contrast, in Reaction Formula 5, when the amount of the carboxyl group used is more than the amount of the glycidyl group used, the reaction is promoted, and the three glycidyl groups of the compound represented by the general formula (i-1) are all The carboxyl group undergoes a ring-opening esterification reaction, and the possibility of producing a compound represented by the following general formula (iv) is extremely high. Since the compound represented by the general formula (iv) has a high molecular weight and has low solubility in liquid crystals, on the other hand, it does not have a glycidyl group having high reactivity with an epoxy curing agent. Therefore, there is a concern that such a compound has low curability and is not suitable as a raw material of a liquid crystal sealing agent.

In order to leave a part of the glycidyl group in the compound represented by the general formula (iii-1) and the compound represented by the general formula (iii-2), it is necessary to stop the reaction at the stage of the desired reaction rate, but it is difficult to precisely at the desired The reaction rate stops the reaction. Therefore, when the reaction formula 5 is carried out, it is preferred to adjust the mixing ratio of the glycidyl group and the carboxyl group in the above manner.

【化37】

X ₄₂ in the above general formula (iv) represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or the above general A group represented by the formula (t2), and R ₉₁ represents a hydrogen atom or a methyl group.

The above reaction rate can be confirmed by a known analysis means. Examples of the above analysis means include a liquid chromatograph, a thin layer chromatography, and an IR analysis device.

The above continuous ring-opening esterification reaction can also be carried out in a solvent-free or solvent inert to such a reaction. Examples of such a solvent include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, a halogen solvent, and a polar solvent.

Examples of the above hydrocarbon-based solvent include n-hexane, benzene, toluene or xylene. Examples of the above ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the above ester solvent include ethyl acetate or butyl acetate. Examples of the above ether solvent include diethyl ether, tetrahydrofuran or dioxane. Examples of the above halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Perclene (general name of tetrachloroethylene). Furthermore, the above polar solvent Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethylammonium, and cyclopentanium. These solvents may be used singly or in combination of plural kinds.

In the above continuous ring-opening esterification reaction, a catalyst which functions in the activation reaction may also be used as needed. Examples of such a catalyst include an organic phosphine compound, a tertiary amine compound, a fourth-order ammonium salt compound, an organic phosphate compound, an imidazole compound, and an organometallic compound.

In the above catalyst, examples of the above organic phosphine compound include triphenylphosphine. Examples of the above tertiary amine compound include triethylamine and triethanolamine. Examples of the above-mentioned fourth-order ammonium salt compound include trimethyl ammonium chloride, and triethyl benzyl ammonium chloride. Examples of the above organic phosphate compound include tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. Examples of the above imidazole compound include 2-methylimidazole. Examples of the above organometallic compound include cobalt octenate. These compounds may be used singly or in combination of plural kinds.

From the viewpoint of obtaining a sufficient reaction rate at the time of the reaction, the amount of the catalyst used is preferably from 0.01 to 10.0% by mass, more preferably from 0.01 to 5.0% by mass, based on the total mass of the reaction mixture of Reaction Formula 5.

The reaction temperature of the above continuous ring-opening esterification reaction is not particularly limited, and only The temperature required for carrying out such a reaction may be sufficient, but it is preferred to keep the above reaction temperature substantially constant in the range of 0 to 200 ° C, more preferably 0 to 150 ° C.

The reaction time of the above-described continuous ring-opening esterification reaction is not particularly limited as long as it is appropriately set depending on the reaction temperature, the amount of the compound to be used, the type and combination of the solvent and the catalyst, the amount to be used, and the like. From the viewpoint of promoting the above reaction, it is preferably from several minutes to several tens of hours.

The method of producing a compound having a glycidyl group and a (meth)acryl fluorenyl group in the molecule by performing a continuous ring-opening esterification reaction as shown in Reaction Scheme 5 is not limited to the above. In other words, as the component (i) as a starting material, in addition to the general formula (i-1), the general formula (i-2), (i-3) or (i-4) can also be used, and as a general In the component (ii) represented by the formula (ii-1), acrylic acid or methacrylic acid can be used in addition to the compound represented by the above formula (ii-1). These compounds can be appropriately selected and used in combination.

The component (a) of the present invention is preferably in the range of 10 to 13 (cal/cm ³ ) ^1/2 of the theoretical solubility parameter (SP value) of Fedors. Regarding the calculation method of the solubility parameter (SP value), there are various methods and calculation methods, but the theoretical solubility parameter used in the present invention should be based on the calculation method conceived by Fedors (refer to the Japanese Society of Learning, vol. 22). , no. 10 (1986) (53) (566) (Journal of Adhesion Society of Japan), etc.). Since the calculation method does not require a density value, the solubility parameter can be easily calculated. The theoretical solubility parameter (SP value) of the above Fedors is calculated by the following formula.

[Number 1] SP value = (Σ △ el / Σ Δvl) ^1/2 where Σ △ el = (△ H - RT), Σ Δvl = sum of the molar volume

When the solubility parameter (SP value) is within the above range, the solubility of the liquid crystal in the compound represented by the above formula (i-1) of the component (a) is small, and the possibility of contaminating the liquid crystal can be suppressed to a low level. Therefore, the display performance of the liquid crystal display panel is improved and is good.

When the compound (a) of the present invention is synthesized using a plurality of compounds as a raw material, the theoretical solubility parameter (SP value) can be calculated based on the sum of the molar fractions of the respective raw materials to be mixed. The theoretical solubility parameter calculated here should be within the above range.

Hereinafter, a component which can be used as a raw material of the liquid crystal sealing agent in combination with the above component (a) will be described.

(b) Thermal latent hardener

The thermal latent curing agent of the present invention means that it is not mixed with an epoxy group or the like even in a state in which such a resin is generally stored (at room temperature, under visible light, etc.) even when it is mixed with a main component such as an epoxy resin. A functional group that reacts but exhibits reactivity with a functional group by heat or light.

By including such a thermal latent curing group in the liquid crystal sealing agent, the viscosity stability of the liquid crystal sealing agent can be improved. Thereby, the viscosity stability of such a liquid crystal sealing agent at room temperature can be kept good, so that the liquid crystal sealing agent can be filled in a screen printing machine or a dispenser, and can be stably used for a long time when the substrate is drawn with a seal pattern. When the usable time of such a liquid crystal sealing agent is increased, the productivity of the liquid crystal display panel in terms of manufacturing can be improved.

Regarding the thermal latent curing agent of the present invention, it is preferably used as the component (a) A thermal latent epoxy curing agent that functions as an epoxy group and a curing accelerator of the epoxy resin (e) described later. The term "thermal latent epoxy resin" means a compound having an epoxy group as a functional group and having thermal potential.

A known hardener can be used as the thermal latent curing agent of the present invention. Among them, an amine-based thermal latent curing agent having an amine group in the molecule is preferred. The amine-based thermal latent curing agent means a compound having an amine group in the molecule and exhibiting thermal potential. The amine-based thermal latent curing agent does not react with the epoxy group at room temperature, but reacts rapidly with the epoxy group by heating. Further, since the cured product obtained by reacting the amine-based thermal latent curing agent with the epoxy resin is generally a crosslinked polymer, the solubility to the liquid crystal is low. The curing rate of the amine varies depending on the type of the amine, the amount of the addition, the type of the epoxy resin, and the like. However, the amine-based thermal latent curing agent which is preferably used in the present invention is not particularly limited, and may be appropriately selected from compounds known as an amine-based thermal latent curing agent.

Preferable examples of the amine-based thermal latent curing agent include: an organic acid diterpene compound, imidazole and a derivative thereof, dicyandiamide, an aromatic amine, an epoxy modified polyamine, and a polyamine urea. . These can be used alone or in combination.

Further, as the thermal latent curing agent, the softening point temperature measured by the melting point or using the ring and ball method is preferably 75 ° C or more. The liquid crystal sealing agent containing the above-mentioned thermal latent curing agent is more excellent in viscosity stability at room temperature, so that the usable time in manufacturing a liquid crystal display panel can be further increased.

The melting point or the softening point temperature measured by the ring and ball method is 75 ° C or higher. Examples of the amine thermal latent curing agent include dicyandiamide compounds, organic acid diterpenes, and imidazole derivatives.

Examples of the above dicyandiamide compound include dicyandiamide (melting point 209 ° C). Examples of the above organic acid dihydrazine include diammonium adipate (melting point 181 ° C), 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (melting point 120 ° C) . Examples of the above imidazole derivatives include: 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine (2,4-diamino-6-[2'- Ethylimidazolyl-(1')]ethyltriazine) (melting point 215 ° C ~ 225 ° C), 2-phenylimidazole (melting point 137 ° C ~ 147 ° C). These compounds may be used singly or in combination of plural kinds.

The amount of the thermal latent curing agent added is preferably from 1 to 25 parts by mass, and more preferably from 5 to 15 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the thermal latent curing agent added is within the above range, the viscosity stability of the liquid crystal sealing agent is further improved. Further, when such a liquid crystal sealing agent is applied to a liquid crystal display panel, the bonding strength between the liquid crystal sealing agent after curing and the substrate is high, and the adhesion reliability of the liquid crystal display panel is improved. The heat latent curing agent used in the present invention is preferably subjected to a high purity treatment by a water washing method, a recrystallization method or the like.

The liquid crystal sealing agent of the present invention comprising such a thermal latent curing agent is useful as a one-liquid type. The one-liquid type liquid crystal sealing agent is a liquid crystal sealing agent which is uniformly mixed in advance before use, such as a main component such as an epoxy resin and a heat-promoting hardening agent, and has excellent storage stability. The excellent storage stability means that the curing reaction is hardly performed even when the liquid crystal sealing agent is stored at room temperature or lower. Specifically, it is preferred to use a liquid crystal sealing agent at The viscosity increase rate at 5 ° C for 5 days is less than or equal to 2 times the viscosity of the liquid crystal sealing agent before storage.

(c) Free radical polymerization initiator

The radical polymerization initiator of the present invention refers to a compound that absorbs light or heat to generate a radical. Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator.

In the present invention, as the component (c), a photoradical polymerization initiator is preferably used. The photoradical polymerization initiator is a compound that generates a radical by irradiation with light, that is, a compound that absorbs light energy and decomposes to generate a radical species. The liquid crystal sealing agent containing such a photoradical polymerization initiator can be hardened by irradiation of light, and when it is used for a liquid crystal dropping method, hardening treatment such as post-hardening is not required, and the hardening time of the liquid crystal sealing agent can be shortened. Therefore, productivity can be improved.

A known compound can be used as the photoradical polymerization initiator, and is not particularly limited. Examples thereof include a benzoin compound, an acetophenone compound, a benzophenone compound, a thioxanthone compound, an α-mercapto oxime ester compound, a benzoin compound, and a benzoin ether compound. A benzoic acid ester compound, a benzyl compound, an azo compound, an anthraquinone compound, a phenyl sulfide compound, a mercaptophosphine oxide compound, an organic dye compound, and an iron-phthalocyanine compound. These can be used alone or in combination.

In the present invention, as described above, a thermal radical polymerization initiator may be used as the component (c). The term "thermal radical polymerization initiator" refers to a compound which generates a radical after heating, that is, it is decomposed and absorbed after absorbing thermal energy. A compound from the base species.

When the liquid radical sealing agent is prepared by using the above-mentioned thermal radical polymerization initiator together with a photoradical polymerization initiator, the substrate is bonded and then temporarily cured by light, and then heated, whereby the film can be heated in a short time. The liquid crystal sealant is sufficiently hardened. In this case, when only the light is applied to cure the liquid crystal sealing agent, the liquid crystal sealing agent remains as an uncured portion in a light-shielding region where light is not directly irradiated. However, if heat is used during curing, the light-shielding region may be used. The liquid crystal sealing agent is hardened to various corners. Therefore, when such a liquid crystal sealing agent is applied to a liquid crystal display panel, a liquid crystal display panel having extremely low liquid crystal contamination and excellent adhesion between the liquid crystal sealing agent and the substrate after curing can be obtained.

As the thermal radical polymerization initiator, a known compound can be used without particular limitation. Examples thereof include an organic peroxide, an azo compound, a substituted ethane compound, a benzoin compound, a benzoin ether compound, and an acetophenone compound.

Examples of organic peroxides include classification into ketone peroxide, peroxy cyclohexane, hydro peroxide, dialkyl peroxide, A compound of a peroxy ester, diacyl peroxide, or peroxy dicarbonate.

Examples of organic peroxides are shown below. The number in parentheses is the 10-hour half-life temperature (refer to the Wako Pure Chemicals catalogue, the catalogue of the Yibo Ai Co., Ltd. and the above-mentioned Polymer Handbook). Examples of the above ketone peroxide compound include methyl ethyl ketone peroxide (109 ° C), a peroxide ring Cyclohexanone peroxide (100 ° C).

Examples of the azo compound include a water-soluble azo-based thermal radical polymerization initiator, an oil-soluble azo-based thermal radical polymerization initiator, and a polymer azo-based thermal radical polymerization initiator.

Examples of the water-soluble azo-based thermal radical polymerization initiator include: 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate (2,2'- Azobis[2-(2-imidazoline-2-yl)propane]disulfatedihydrate) (46 ° C), hydrated 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate)(57°C), 2,2'-azobis{2-[1-(2-hydroxyethyl)-2- Imidazolin-2-yl]propane} dihydrochloride (2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazoline-2-yl]propane}dihydchloride) (60 ° C), 2 , 2'-azobis(1-imino-1-pyrrolidin-2-ethylpropane) dihydrochloride (2,2'-azobis(1-imine-1-pyrrolidino-2-ethylpropane}methylpropionamidine ]dihydchloride) (67 ° C), 2,2'-azobis[2-methyl-N-(2-carboxyethyl)propanamide] (2,2'-azobis[2-methyl-N-( 2-hydroxyethyl)propionamide]) (87 ° C), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (2,2'-azobis[2-( 2-imidazoline-2-yl)propane]dihydchloride) (44 ° C), 2,2'-azobis(2-methylpropionamidine) dihydchloride ) (56 , 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (2,2'-azobis[2-(2-imidazoline-2-yl)propane]) (61 ° C ), 2, 2'- Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamine} (2,2'-azobis{2-methyl-N-[1, 1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}) (80 ° C)

Examples of the oil-soluble azo-based thermal radical polymerization initiator include: 2,2'-azobis(4-methoxy-2,4'-dimethylvaleronitrile) (2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile)) (30 ° C), dimethyl-2,2'-azobis(2-methylpropionate) ) (66 ° C), 1,1 '-azobis (cyclohexane-1-carbonitrile) (88 ° C), 1,1 '-[( 1,1'-[(cyano-1-methylethyl)azo]formamide (104 ° C), 2,2'-azobis (N- 2,2'-azobis(N-cyclohexyl-2-methylpropionamidine) (111 ° C), 2,2'-azobis(2,4'-dimethylpentyl) 2,2'-azobis(2,4-dimethylvaleronitrile) (51 ° C), 2,2'-azobis(2-methylbutyronitrile) (2,2'-azobis(2-methylbutyronitrile) (67 ° C), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide] (2,2'-azobis[N-(2-propenyl)-2- Methylpropionamide]) (96 ° C), 2,2'-azobis(N-butyl-2-methylpropionamide) (1,2'-azobis (N-butyl-2-methylpropionamide)) (110 ° C) ).

Examples of the polymer azo-based thermal radical polymerization initiator include a polymer azo-based thermal radical polymerization initiator containing a polydimethylsiloxane unit, and a polyethylene glycol-containing unit. (Polyethyleneglycol unit) polymer azo thermal radical polymerization initiator. Further, these thermal radical polymerization initiators may be used singly or in combination of plural kinds.

The amount of the component (c) to be added is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the liquid crystal sealing agent, regardless of whether the type of energy generating the radical is light or heat. When the amount of the radical polymerization initiator added is 0.01 parts by mass or more, such a liquid crystal sealing agent can be cured in a short time by irradiating the liquid crystal sealing agent with light or heat appropriately selected. In addition, when the amount of the component (c) added is 5 parts by mass or less, the coating property of the liquid crystal sealing agent is good, and a hardened product which is uniformly hardened can be obtained by light irradiation.

(d) filler

The filler of the present invention is a filler which is used for the purpose of improving the viscosity of the liquid crystal sealing agent, improving the strength of the cured product obtained by curing the liquid crystal sealing agent, or suppressing the linear expansion property to improve the adhesion reliability of the liquid crystal sealing agent. .

The filler preferably used in the present invention is not particularly limited, and includes a known filler generally used in the field of electronic materials. Examples of the filler include: calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum citrate, zirconium silicate, iron oxide, titanium oxide, alumina (alumina), zinc oxide, cerium oxide, potassium titanate, kaolin , talc powder, asbestos powder, quartz powder, mica, glass fiber, glass beads, sericite activated clay, bentonite, aluminum nitride, tantalum nitride and other inorganic fillers.

As the filler of the present invention, polymethyl methacrylate or polystyrene may be used as long as it does not impair the characteristics of the liquid crystal sealing agent. A known organic filler such as a copolymer obtained by copolymerization of a monomer of the above polymer and another monomer, a polyester fine particle, a polyurethane fine particle, and a rubber fine particle.

Among them, an inorganic filler is preferred from the viewpoint of improving the coefficient of linear expansion and shape retention. Among the above inorganic fillers, cerium oxide and talc are more preferable from the viewpoint of high UV permeability. Further, the filler used in the liquid crystal sealing agent of the present invention may be a material which is graft-modified with an epoxy resin, a decane coupling agent or the like, regardless of the inorganic or organic filler.

The shape of the filler is not particularly limited, and may be any of a shaped object such as a spherical shape, a plate shape, and a needle shape, or an amorphous material. The maximum particle diameter of the filler is preferably 6 μm or less, more preferably 2 μm or less. The particle size of the filler can be measured by a laser diffraction method. When a liquid crystal sealing agent containing a filler having the above particle diameter is used in the method of manufacturing a liquid crystal display panel, it is possible to form a liquid crystal cell having a very good dimensional stability of a cell gap.

The amount of the filler added is preferably from 1 to 40 parts by mass, more preferably from 10 to 30 parts by mass, per 100 parts by mass of the liquid crystal sealing agent other than the filler. The liquid crystal sealing agent adjusted in such a manner that the amount of the filler added was excellent in the coating property on the substrate. The filler may also be used in combination with the photocurable resin. In this manner, the liquid crystal sealing agent used in combination with the filler and the photocurable resin is excellent in photocurability and hardens in a short time. Also, the width of the box pitch is kept slightly, so the dimensional stability becomes good.

The liquid crystal sealing agent of the present invention may further comprise either (e) an epoxy resin and (f) an acrylic compound, or (e) an epoxy resin and (f) an acrylic compound.

(e) Epoxy resin

The epoxy resin of the present invention means a compound having one or more epoxy groups in the molecule. Examples of the epoxy resin which is preferably used in the liquid crystal sealing agent of the present invention include an aromatic polyglycidyl ether compound, a phenol resin, a novolac type polyglycidyl ether compound, and a glycidyl ether compound.

Examples of the aromatic polyglycidyl ether compound include an aromatic diol compound and a glycol compound obtained by modifying various diols with epichlorohydrin. Compound. Examples of the aromatic diol compound include a bisphenol A type epoxy resin, a bisphenol S type epoxy resin, a bisphenol F type epoxy resin type, and a bisphenol AD epoxy resin. Examples of the above glycol include ethylene glycol, propylene glycol, and alkylene glycol.

Examples of the above phenol resin include a compound obtained by deriving phenol or cresol with formaldehyde. Examples of the phenolic polyhydric glycidyl ether compound include a compound obtained by reacting a polyphenol represented by a polyalkenylphenol or a copolymer thereof with epichlorohydrin. Further, examples of the above glycidyl ether compound include a benzene dimethylphenol resin.

Among them, examples of preferred (e) epoxy resins include: cresol novolac type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type ring Oxygen resin, trisphenol ethane type epoxy resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin. Examples of particularly preferred epoxy resins include acrylic rubber modified epoxy resins of the above epoxy resins. In the liquid crystal sealing agent of the present invention, the above epoxy resins may be used singly or in combination of plural kinds.

The epoxy resin used in the present invention preferably has a softening point temperature of 40 ° C or more as measured by a ring and ball method, and more preferably has a weight average molecular weight of 1,000 to 10,000. Such an epoxy resin has low solubility and diffusibility to liquid crystals. Therefore, the liquid crystal display panel manufactured using the liquid crystal sealing agent using such an epoxy resin has good display property.

The weight average molecular weight of the epoxy resin can be measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard. Further, as the epoxy resin, an epoxy resin which is highly purified by a molecular distillation method or the like and has impurities removed is preferably used.

The amount of the epoxy resin added is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. Such a liquid crystal sealing agent is excellent in heat resistance. On the other hand, when the amount added is less than 5 parts by mass, the curing rate is slow, and when it exceeds 50 parts by mass, the heat resistance of the liquid crystal sealing agent may be lowered.

(f) Acrylic compound

The acrylic compound of the present invention means a compound having one or more acrylic groups in the molecule. The acrylic compound of the present invention also contains a (meth)acrylic resin such as a methacrylic resin. Examples of the acrylic compound include acrylate and/or methacrylate monomers or oligomers thereof, but are not particularly limited and include known compounds. The liquid crystal sealing agent containing the above-mentioned acrylic compound is excellent in water resistance, and therefore, if it is applied to a liquid crystal display panel, the bonding strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel can be extremely high, and A high-quality liquid crystal display panel with excellent moisture resistance reliability.

Preferable examples of the component of the acrylic compound (f) include the following.

The above substances include: diacrylate and/or dimethacrylate of polyethylene glycol, propylene glycol, polypropylene glycol, etc.; diacrylate and/or dimethacrylate of tris(2-hydroxyethyl)isocyanate; a diacrylate and/or dimethacrylate of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 4 moles of neopentyl glycol; a diacrylate and/or dimethacrylate of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to bisphenol A; adding 3 to 1 mole of trimethylolpropane a diacrylate or triacrylate and/or dimethacrylate or trimethacrylate of a triol obtained by mole or more than 3 moles of ethylene oxide or propylene oxide; Diacrylate and/or dimethacrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to phenol A; tris(2-hydroxyethyl)isocyanate Triacrylate and/or trimethacrylate; trimethylolpropane triacrylate and/or trimethacrylate or oligomer thereof; pentaerythritol III Polyester and/or trimethacrylate or oligomer thereof; polyacrylate and/or polymethacrylate of dipentaerythritol; tris(propylene oxyethyl)isocyanate; caprolactone modified tris(propylene Hexaoxyethyl)isocyanate; caprolactone modified tris(methacryloyloxyethyl)isocyanate; polyacrylate and/or polymethacrylate of alkyl modified dipentaerythritol; caprolactone modified dipentaerythritol Polyacrylate and/or polymethacrylate; hydroxytrimethylacetic acid neopentyl glycol diacrylate and/or dimethacrylate; caprolactone modified hydroxytrimethylacetic acid neopentyl glycol diacrylate Ester and / or dimethacrylate; ethylene oxide modified phosphoric acid acrylate and / or dimethacrylate; ethylene oxide modified alkylation phosphorus Acid acrylate and/or dimethacrylate; neopentyl glycol, trimethylolpropane, oligoacrylate of pentaerythritol and/or oligomeric methacrylate.

Further, examples of the component of the acrylic compound (f) include: a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a trisphenol methane type epoxy resin. All epoxy groups such as a resin, a trisphenol-ethane epoxy resin, a trisphenol epoxy resin, a dicyclopentadiene epoxy resin, and a biphenyl epoxy resin are reacted with a (meth) acrylate to obtain A resin that completely oxidizes the epoxy resin with (meth) propylene. These compounds may be used singly or in combination of plural kinds.

When the acrylic compound (f) component is contained in the liquid crystal sealing agent, it is preferably used in combination with the epoxy resin (e) component. The amount of the component (e) added is preferably 20 to 200 parts by mass based on 100 parts by mass of the component (f). When the liquid crystal sealing agent is cured by light or heat, a cured product having a high glass transition temperature (Tg) can be obtained. The Tg of the cured product of the liquid crystal sealing agent can be measured by a dynamic viscoelasticity measuring device (DMA). For the purpose of obtaining a high-purity liquid crystal sealing agent or the like, the component (f) is preferably a material which is highly purified by a water washing method or the like.

Examples of the (meth)acryl fluorene-modified epoxy resin preferably used in the present invention include, for example, a resin obtained by reacting an epoxy resin with (meth)acrylic acid or phenyl methacrylate in the presence of a basic catalyst. . Examples of the above epoxy resin include a bisphenol type epoxy resin and a novolac type epoxy resin.

The (meth) acrylate-modified epoxy resin having both an epoxy group and a (meth)acrylic group in the skeleton exhibits high compatibility with the component (e). Therefore, containing (meth) propylene ruthenium modified ring The liquid crystal sealing agent of the oxygen resin and the component (e) is high in glass transition temperature (Tg), and is excellent in durability and heat resistance. Further, the bonding strength between the cured product of the liquid crystal sealing agent and the substrate constituting the liquid crystal display panel becomes high.

Examples of the epoxy resin as a raw material of the (meth)acryl oxime-modified epoxy resin include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a bisphenol A type epoxy resin, and a bisphenol F type ring. Oxygen resin, trisphenol methane type epoxy resin, trisphenolethane type epoxy resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin. Further, the (meth)acrylomer-modified epoxy resin is preferably purified by a molecular distillation method, a washing method, or the like.

(g) Other additives

Further, in the liquid crystal sealing agent of the present invention, an additive may be included as needed. Examples of the additive preferably used in the present invention include a thermal radical polymerization initiator, a coupling agent such as a decane coupling agent, an ion trapping agent, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer, and an antifoaming agent. The above additives may be used singly or in combination of two or more depending on the use.

In order to secure the pitch of the liquid crystal cell, a gap control material or the like may be included. The gap control material may be included in the liquid crystal sealing agent, or may be applied to a substrate constituting the liquid crystal display panel in advance.

An organic solvent may be included in the preparation of the thermosetting sealant to improve dispensing coatability or screen printing property. Such an organic solvent preferably has high compatibility with the epoxy resin of the component (e), a boiling point of 140 to 220 ° C, and is inert to the epoxy group. Examples of the above organic solvent include a ketone solvent, an ether solvent, and an acetate solvent. The above thermal latent hardener can be single Use it alone or in combination.

[Preparation method of liquid crystal sealing agent]

The method for preparing the liquid crystal sealing agent of the present invention is not particularly limited, and a known technique can be used. The apparatus for mixing the components in the liquid crystal sealing agent is not particularly limited, and examples thereof include a two-arm type agitator, a roll type kneader, a twin-screw extruder, a ball mill, and a planetary mixer, and a known kneading machine can be used. . The liquid crystal sealing agent which was appropriately mixed by any of the methods was filtered with a filter to remove impurities. Then, after vacuum defoaming treatment, it is sealed and filled in a glass bottle or a polymer container, and stored and transported as needed.

[Manufacturing Method of Liquid Crystal Display Panel]

Next, a method of manufacturing the liquid crystal display panel of the present invention will be described. The liquid crystal sealing agent of the present invention described above can be applied to any of a liquid crystal injection method and a liquid crystal dropping method. Hereinafter, a method of manufacturing the liquid crystal display panel of the present invention related to the liquid crystal injection method and the liquid crystal dropping method will be described in order.

In the method for manufacturing a liquid crystal display panel of the present invention, a liquid crystal display panel is manufactured by laminating two opposing substrates by a liquid crystal sealing agent, and the method includes: (1) a process of preparing one or more substrates, the substrate a frame-shaped display region formed in such a manner that a pixel arrangement region is surrounded by the liquid crystal sealing agent of the present invention; (2) a process of injecting liquid crystal into the display region in an uncured state or on another substrate; (3) a process in which a liquid crystal substrate is overlapped with another substrate; and (4) a liquid crystal sealing agent sandwiched between the two substrates is irradiated with light and heated, or only irradiated light and added One of the hot processes.

In the process of (1), a liquid crystal sealing agent is applied to any of the two substrates, and a substrate having a frame-shaped display region is disposed. Here, the frame made of the liquid crystal sealing agent is formed such that the pixel arrangement region is surrounded.

As the above liquid crystal sealing agent, the liquid crystal sealing agent relating to the present invention described above is useful. The liquid crystal sealing agent not only forms a frame for a display region or the like, but also serves as an adhesive for bonding the two substrates at a predetermined interval. Further, the method of applying the liquid crystal sealing agent to the substrate is not particularly limited, and examples thereof include coating using a dispenser or coating using screen printing, and a known technique may be used. When manufacturing a small liquid crystal display panel, it is preferable to apply by screen printing from the viewpoint of improving productivity.

Examples of the two substrates used in the liquid crystal display panel include a glass substrate on which a matrix TFT is formed or a substrate on which a color filter and a black matrix are formed. Examples of the substrate material include: glass or polycarbonate, polyethylene terephthalate, polyether oxime, polymethyl methacrylate (PMMA) and the like.

An alignment film can be formed on the surface opposite to each substrate. The alignment film is not particularly limited, and for example, an alignment film composed of a known organic alignment agent or inorganic alignment agent can be used. Further, the gap control material may be dispersed in advance on the substrate. The gap control material generally uses true spherical cerium oxide particles, which is effective in keeping the cell pitch constant. Generally, an inner surface gap controlling material or a gap controlling material contained in the liquid crystal sealing agent which is previously spread on the substrate is used. Further, the type and size of the gap control material are not particularly limited, and a known gap control material may be used depending on the desired size of the cell pitch or the like.

In the process of (2), an appropriate amount of liquid crystal is dripped onto the inside of the frame which is the display region of the uncured state or another substrate. Here, the other substrate in which the liquid crystal is dropped refers to a substrate different from the substrate including the display region. When liquid crystal is dripped onto another substrate, when the substrates are overlapped with each other, liquid crystal can be dripped into a region which can be used as a display region.

Further, regarding the liquid crystal to be dripped, it is preferable to adjust the dripping amount of the liquid crystal according to the size of the frame so that the dripped liquid crystal is stored in the frame. When the liquid crystal is dripped into the frame in this manner, the capacity of the liquid crystal does not exceed the capacity of the empty box surrounded by the bonded frame and the substrate. Therefore, no excessive pressure is applied to the frame, so that the seal forming the frame is not broken.

In the process of (3), the substrate in which the liquid crystal is dropped is overlapped with the other substrate. Here, the superposition is preferably carried out under reduced pressure by a vacuum bonding apparatus or the like. By returning the two substrates superposed under reduced pressure to atmospheric pressure in a subsequent process, the substrates can be bonded to each other by the difference in gas pressure.

In the process of (4), the liquid crystal sealing agent sandwiched between the two substrates is irradiated with light and heated, or only one of irradiation light and heating is performed. Thereby, a radical is generated in the inside of the liquid crystal sealing agent by the action of the radical polymerization initiator, and the hardening reaction between the main component and the hardener is promoted, so that the hardening of the liquid crystal sealing agent proceeds.

In the process of the above (4), the type of light to be irradiated to the liquid crystal sealing agent, the irradiation time, the temperature or time during heating, and the like are not particularly limited, and may be appropriately selected depending on the composition of the liquid crystal sealing agent. For example, when the liquid crystal sealing agent is cured by heat, from the viewpoint of promoting the curing of the liquid crystal sealing agent, the heating temperature is preferably 40 to 90 ° C, and the heating time is 1 to 120 minutes. this In addition, the liquid crystal sealing agent may be heat-hardened as needed, and then post-hardened at 110 to 150 ° C for 30 to 90 minutes. The heating means of the liquid crystal sealing agent is not particularly limited, and examples thereof include well-known heating devices such as an oven, a hot plate, and a hot press.

The invention may also include a process of returning the two stacked substrates from the reduced pressure plate to the atmospheric pressure after the (3) process. When the two substrates superposed under reduced pressure are returned to the atmospheric pressure under reduced pressure, a difference in pressure is generated between the inside and the outside of the frame. Therefore, the two substrates are pressed from both outer sides to bond the substrates to each other.

Further, in recent liquid crystal dropping methods, in order to achieve an improvement in productivity, a plurality of frames are formed on a substrate by a liquid crystal sealing agent, and after bonding two substrates, the liquid crystal display panel is cut into individual liquid crystal display panels by cutting the outer periphery of the frame. Methods. The invention is also suitable for such a method.

The liquid crystal sealing agent of the present invention has high viscosity stability, low solubility to liquid crystals, and contains a component (a) having high curability, a hardening agent having thermal potential, a radical polymerization initiator, and a filler. When a liquid crystal display panel is produced by the liquid crystal dropping method using such a liquid crystal sealing agent, even if there is a light-shielding region, it can be sufficiently cured, and work can be performed while maintaining high storage stability and high coating property. As a result, the uncured portion of the cured product of the liquid crystal sealing agent is extremely small, and as a result, a liquid crystal display panel having high adhesion strength between the cured product of the liquid crystal sealing agent and the substrate can be obtained.

The degree of liquid crystal contamination of the liquid crystal display panel, that is, the liquid crystal contamination of the liquid crystal display panel can be evaluated by the difference of the NI point, that is, the ΔNI point. NI point refers to liquid The temperature at which a crystal transitions from a nematic phase to an isotropic phase (isotropic phase). The phase transition temperature is measured using a differential thermal analyzer from the turning point of the exothermic peak. The ΔNI point is the difference between the "NI point of uncontaminated liquid crystal" and the "NI point of contaminated liquid crystal". When a raw material having a high liquid crystal contamination or a liquid crystal sealing agent is mixed with a liquid crystal, the absolute value of the ΔNI point becomes large. On the other hand, when the liquid crystal contamination of the raw material or the liquid crystal sealing agent is low, the absolute value of the ΔNI point becomes low. Therefore, the smaller the ΔNI point, the lower the liquid crystal contamination.

[Examples]

Hereinafter, the present invention will be described in more detail by exemplifying the examples and comparative examples of the present invention. However, the invention is not limited to the manner shown therein.

(a) a compound having a (meth) acrylonitrile group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2,000

As the component (a), the compounds synthesized in the following Synthesis Examples 1 to 10 were used, respectively. Among them, the compounds synthesized in Synthesis Examples 1 to 4 correspond to the first component (a), and the compounds synthesized in Synthesis Examples 7 to 10 correspond to the second component (a). Further, the compounds synthesized in Synthesis Examples 5 and 6 have a predetermined organic group in the molecule, but the number average molecular weight thereof exceeds the range of 500 to 2,000.

In each of the synthesis examples, the acid value of the reaction mixture taken at any stage during the synthesis was calculated by the following method, and the synthesis reaction was carried out while confirming the progress of the reaction based on the calculation of the value of the acid value. The acid value is such that a sample taken from the reaction mixture is dissolved in diethyl ether. An ethanol solution, and added to a phenolphthalein ethanol solution, and an aqueous solution of KOH (0.1 N) is added dropwise until the resulting solution becomes colorless, based on the amount of KOH consumed. Calculate.

Further, the number average molecular weight of the final target obtained in each synthesis example was measured by the following method. The number average molecular weight is determined using 1) gel permeation chromatography (GPC) based on polystyrene standards and 2) field desorption mass spectrometry (FD. MS method).

[Synthesis Example 1]

In Synthesis Example 1, a compound A1 containing a (meth)acryl fluorenyl group and a glycidyl group was synthesized by reacting glycidyl acrylate methacrylate modified phthalic acid with bisphenol F diglycidyl ether.

First, 74 g (0.5 mol) of phthalic anhydride and 271 g (0.5 mol) of glycidyl acrylate methacrylate were mixed as a catalyst in a 500 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. 0.7 g of tributylammonium bromide and 0.5 g of phenothiazine as a polymerization inhibiting agent were heated to 80 ° C and reacted for 1 hour, and further heated to 130 ° C for two hours.

276 g (0.4 mol) of the reaction product, 125 g (0.4 mol) of a bisphenol F-type epoxy resin (Epotohto YDF-8170 Tosoh Chemical Co., Ltd.), and 0.6 g of tributylammonium bromide as a catalyst were used. 0.1 g of hydroxymonomethylether of a polymerization inhibiting agent was placed in a 500 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube, and heated and mixed at 80 ° C, and then the dry air was blown into the reaction. Until the acid value is made 2 mgKOH/g or less. Then, the reaction product column was separated using tannin to obtain Compound A1. The result of HPLC and NMR analysis of the obtained Compound A1 was confirmed to be a compound containing a (meth) propylene group and a glycidyl group.

Further, the number average molecular weight of the compound A1 was measured by GPC, and the number average molecular weight of the compound A1 measured as a single peak was 689. Further, the number average molecular weight of the compound A1 was measured by the FD-MS method, and the single molecular weight was the same molecular weight (689).

[Synthesis Example 2]

In Synthesis Example 2, 4-methylpropenyl methoxyethyl trimellitic acid modified with 2-hydroxyethyl acrylate was reacted with bisphenol F diglycidyl ether by the following method to synthesize inclusion ( Methyl)propenyl and glycidyl compound A2.

First, 152 g (0.5 mol) of 4-methylpropenyloxyethyl trimellitic acid and 2-hydroxyethyl methacrylate were mixed in a 1000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. 58 g (0.5 mol), 0.7 g of tributylammonium bromide as a catalyst, and 0.5 g of phenothiazine as a polymerization inhibitor, were heated to 80 ° C and reacted for 1 hour, and further heated to 130 ° C for two hours. Then, 168 g (0.4 mol) of this reaction product, 125 g (0.4 mol) of bisphenol F-type epoxy resin (made by Epotohto YDF-8170 Tosei Chemical Co., Ltd.), and tributylammonium bromide as a catalyst were 0.6 g. 0.1 g of hydroxymonomethylether as a polymerization inhibitor was placed in a 500 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube. After the obtained mixture was heated to 80 ° C, the dry air was blown into the surface while allowing the reaction to proceed until the acid value was 2 mgKOH/g or less.

The reaction mixture was diluted with 1000 g of ethyl acetate, washed with water and dried over five times of ultrapure water. Then, the reaction product column was separated using tannin to obtain Compound A2. HPLC, NMR fractionation of the obtained Compound A2 As a result of the analysis, it was confirmed to be a compound containing a (meth) acrylonitrile group and a glycidyl group. Further, as a result of GPC analysis of the compound A2, the number average molecular weight of the compound A2 measured as a single peak was 733. It was confirmed that the number average molecular weight of the compound A2 was the same molecular weight in the FD-MS method at the single peak.

[Synthesis Example 3]

In Synthesis Example 3, a compound A3 containing a methacryl fluorenyl group and a glycidyl group was synthesized by reacting 2-hydroxy methacrylate-modified phthalic acid with bisphenol F diglycidyl ether by the following method.

First, 74 g (0.5 mol) of phthalic anhydride and 65 g (0.5 mol) of 2-hydroxyethyl methacrylate were mixed in a 500 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube, and used as a catalyst. 0.7 g of tetrabutylammonium bromide and 0.5 g of phenothiazine as a polymerization inhibiting agent were heated to 80 ° C and reacted for 1 hour, and further heated to 130 ° C for two hours. After the reaction, the reaction mixture was diluted with 1000 g of ethyl acetate. 111 g (0.4 mol) of the reaction product, 125 g (0.4 mol) of a bisphenol F type epoxy resin (Epotohto YDF-8170 Tosoh Chemical Co., Ltd.), and 0.6 g of tributylammonium bromide as a catalyst were used. 0.1 g of hydroxymonomethylether of a polymerization inhibiting agent was placed in a 500 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube. After the obtained mixture was heated to 80 ° C, the dry air was blown into the surface while allowing the reaction to proceed until the acid value was 2 mgKOH/g or less.

The reaction mixture was diluted with 1000 g of ethyl acetate, washed with water and dried over five times of ultrapure water. Then, the reaction product column is separated using tannin extract, Compound A3 was obtained. The composition of the obtained compound A3 was analyzed by HPLC and NMR, and it was confirmed that it was a compound containing a methacrylinyl group and a glycidyl group. Further, as a result of GPC analysis of the compound A3, the number average molecular weight of the compound A3 measured as a single peak was 591. It was confirmed that the number average molecular weight of the compound A3 was the same molecular weight in the FD-MS method at the single peak.

[Synthesis Example 4]

In Synthesis Example 4, a compound A4 containing a (meth) acrylonitrile group and a glycidyl group was synthesized by reacting a carboxylic acid derivative with bisphenoxyethanol hydrazine diglycidyl ether.

First, a 2-hydroxyethyl acrylate 6-caprolactone addition (manufactured by Daicel Chemical Industry Co., Ltd., trade name PLACCELFA3) was purified by using a silicone rubber. In a 1000 ml five-necked flask equipped with a stirrer, an air guide tube, a thermometer, a cooling tube, and a funnel tube, 48 g of sodium hydride and 200 g of toluene were placed, and the mixture was ice-cooled under a nitrogen stream. A solution obtained by dissolving 229 g (0.5 mol) of the purified 2-hydroxyethyl acrylate 6-caprolactone in 200 g of toluene was dropped over two hours.

Then, while the reaction mixture after the completion of the dropwise addition of the solution was kept for one hour, the reaction mixture was filtered to remove unreacted sodium hydride. Thereafter, 185 g (2 mol) of epichlorohydrin, 5 g of tetramethylammonium hydroxide (TMAH), and 0.1 g of hydroxymonomethylether were added to the reaction mixture, and after mixing, dry air was blown in. It was stirred at 70 ° C for 3 hours.

Thereafter, the reaction mixture after the end of the reaction was washed 5 times with ultrapure water. Thereafter, the pressure is reduced by heating at 120 ° C to remove impurities such as excess epichlorohydrin, thereby obtaining a reaction product of a 6-caprolactone addition of 2-hydroxyethyl acrylate and epichlorohydrin (A4a). . Next, the reaction product (A4a) (0.4 mol) and 6-((6-acryloyloxy)hexyloxy)hexanoic acid (ALONIX M-5300 East Asia Synthetic Co., Ltd.) purified in advance by column chromatography were mixed. (molecular weight: 300), 120 g (0.4 mol), 0.6 g of tributylammonium bromide as a catalyst, and 0.1 g of hydroxymonomethylether as a polymerization inhibitor, and heated to 80 ° C The reaction product (A4b) was obtained by blowing dry air to one side and reacting it until the acid value was 2 mgKOH/g or less.

Next, 163 g (0.2 mol) of the obtained reaction mixture (A4b), 61 g (0.2 mol) of 4-methylpropenyloxyethyl trimellitic anhydride, and 0.5 g of phenothiazine as a polymerization inhibitor were mixed and heated to 80 ° C. The reaction was carried out for 1 hour, and further heated to 130 ° C for two hours to obtain a reaction product (A4c). Then, 112 g (0.1 mol) of this reaction product (A4c), bisphenoxyethanol hydrazine diglycidyl ether (manufactured by BPEF-G Osaka Gas Chemical Co., Ltd., molecular weight 550), 55 g (0.1 mol), as a catalyst 0.2 g of tributylammonium bromide and 0.1 g of hydroxymonomethylether as a polymerization inhibiting agent were placed in a 300 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube, and mixed, and then heated to 80 ° C. . The dry air was blown into one side and allowed to react until the acid value was 2 mgKOH/g or less. Then, the reaction product column was separated using tannin to obtain a compound A4.

The result of HPLC and NMR analysis of the obtained compound A4 was confirmed to be a compound containing a (meth) propylene group and a glycidyl group. In addition, the result of GPC analysis of the compound A4 was as a single peak (single The number average molecular weight of the compound A4 measured by peaked was 1670. Further, it was confirmed that the number average molecular weight of the compound A4 is the same molecular weight in a single peak in the FD-MS method.

[Synthesis Example 5]

In Synthesis Example 5, an epoxy resin in which a bisphenol A type epoxy resin was modified with a methacrylonitrile group was synthesized.

A bisphenol A type epoxy resin (Epiclon 850RP manufactured by Dainippon Ink Chemical Co., Ltd.) was mixed in a 500-ml flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube. 175 g, methacrylic acid: 43 g, triethanolamine as a catalyst: 0.2 g, hydroxymonomethylether (0.2 g) as a polymerization inhibiting agent, while heating and stirring at 110 ° C for 5 hours while blowing dry air A methacrylonitrile-based modified bisphenol A type epoxy resin was obtained. The obtained resin was subjected to a washing treatment 12 times with ultrapure water to obtain a compound A5. As a result of HPLC and NMR analysis of the obtained compound A5, it was confirmed that 50% of the epoxy group contained was a bisphenol A type epoxy resin modified with a methacryl oxime group. Further, as a result of GPC analysis of the obtained Compound A5, the number average molecular weight was 427.

[Synthesis Example 6]

In Synthesis Example 6, an epoxy resin in which a bisphenol F-type epoxy resin was propylene-based modified was synthesized.

Mixing bisphenol F-type epoxy resin in a 500-ml flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube (Epiclon 850RP Dainippon Ink Chemical Industry Co., Ltd.) 175 g, acrylic acid: 37 g, triethanolamine as a catalyst: 0.2 g, hydroxymonomethylether (0.2 g) as a polymerization inhibitor, while heating and stirring at 110 ° C for 12 hours while blowing dry air An acrylonitrile-based modified bisphenol F-type epoxy resin was obtained. The obtained resin was washed repeatedly 12 times with ultrapure water. As a result of HPLC and NMR analysis of the resin, it was confirmed that 50% of the epoxy group contained was a bisphenol F-type epoxy resin (compound A6) modified with an acrylonitrile group. Further, as a result of GPC analysis of the obtained Compound A6, the number average molecular weight was 412.

[Synthesis Example 7]

In Synthesis Example 7, a compound A7 containing a (meth)acrylonyl group and a glycidyl group was synthesized by reacting a phenol novolry type trifunctional epoxy resin with a (meth)acrylic acid derivative.

First, a phenol novolac type trifunctional epoxy resin (SR-HP3 Sakamoto Pharmaceutical Industry Co., Ltd. (SR-HP3) is added to a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. Manufactured by the method of FD-MS, the average molecular weight of 414) was 142.4 g (0.3 mol), 20.7 g (0.3 mol) of methacrylic acid, 73.3 g (0.3 mol) of the compound B1 described later, and tributyl bromide as a catalyst. 1.45 g of ammonium and 0.01 g of phenothiazine as a polymerization inhibitor were heated and mixed at 80 ° C, and the dry air was blown while being allowed to react for 15 hours until the acid value was 2 mgKOH/g or less. The compound B1 used herein is a reaction product of 2-hydroxyethyl methacrylate and succinic anhydride.

The reaction liquid obtained by diluting 900 g of toluene and 300 g of ethyl acetate 232g. The diluted reaction solution was washed 10 times with 300 g/times of ultrapure water, and concentrated until the conductivity of the aqueous phase became 1 μS/cm or less, thereby obtaining 222 g of a compound. As a result of FD-MS analysis of the obtained Compound A7, the number average molecular weight was 804.

[Synthesis Example 8]

In Synthesis Example 8, an epoxy resin containing a (meth) acrylonitrile group and a glycidyl group was synthesized by reacting a phenol novolak type tetrafunctional epoxy resin with a (meth)acrylic acid derivative.

First, a phenol novolac type 4-functional epoxy resin (YL-7284 Japanese epoxy resin) as a compound represented by the above general formula (i-2) was placed in a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. Company (stock) system, number average molecular weight 636) 318 g (0.5 mol), compound B1 104 g (0.45 mol) described later, and compound B2 110 g (0.45 mol), 2.1 g of tributylammonium bromide as a catalyst, as a polymerization The phenothiazine of the inhibitor was 0.05 g, and the mixture was heated and mixed at 80 °C. The dry air was blown into the surface for 15 hours until the acid value was 2 mgKOH/g or less. The compound B2 used herein is a reaction product of 4-hydroxybutyl acrylate and succinic anhydride.

The obtained reaction liquid was diluted 530 g with 1200 g of toluene and 600 g of ethyl acetate. Then, the operation of washing the diluted reaction liquid with 500 g/times of ultrapure water was repeated 10 times, and the concentration was adjusted until the conductivity of the aqueous phase became 1 μS/cm or less, thereby obtaining 509 g of the compound A8. As a result of FD-MS analysis of the obtained Compound A8, the number average molecular weight was 1111.

[Synthesis Example 9]

In Synthesis Example 9, a phenol novolone type 4-functional ring was obtained by the following method. The oxy resin is reacted with a (meth)acrylic acid derivative to synthesize an epoxy resin containing a (meth) acrylonitrile group and a glycidyl group.

A phenol novolac type 4-functional epoxy resin (YL-7284 Japan Epoxy Resin Co., Ltd.) as a compound represented by the above general formula (i-2) was placed in a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. The system has a number average molecular weight of 636) 318 g (0.5 mol) of FD-MS, 425 g (0.9 mol) of the compound B3 described later, 2.1 g of tributylammonium bromide as a catalyst, and phenothiazine as a polymerization inhibitor. 0.05 g, and the mixture was heated and mixed at 80 ° C, and the dry air was blown into the surface for 15 hours until the acid value was 2 mgKOH/g or less. The compound B3 used herein is a reaction product of caprolactone 3 molar modified methacrylate and succinic anhydride.

The obtained reaction liquid was diluted with 1200 g of toluene and 600 g of ethyl acetate. Then, the operation of washing the diluted reaction liquid with 600 g/times of ultrapure water was repeated 10 times, and the concentration was adjusted until the conductivity of the aqueous phase became 1 μS/cm or less, whereby 730 g of the compound A9 was obtained. As a result of FD-MS analysis of the obtained compound A9, the number average molecular weight was 1770.

[Synthesis Example 10]

In Synthesis Example 10, an epoxy resin containing a (meth)acryl fluorenyl group and a glycidyl group was synthesized by reacting a trifunctional epoxy resin with a (meth)acrylic acid derivative.

Into a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube, a trifunctional epoxy resin VG-3102 (manufactured by Mitsui Chemicals Co., Ltd.), FD-, which is a compound represented by the above general formula (i-4), was charged. The number average molecular weight of the MS method is 460) 184 g (0.40 mol), and the compound B1 described later 92 g (0.40 mol) and Compound B2 97 g (0.40 mol), 2.0 g of tributylammonium bromide as a catalyst, and 0.05 g of phenothiazine as a polymerization inhibitor, were heated and mixed at 80 °C. The dry air was blown into the surface while allowing to react for 8 hours until the acid value was 2 mgKOH/g or less.

The obtained reaction liquid was diluted with 370 g of toluene (900 g) and ethyl acetate (300 g). Then, the diluted reaction solution was washed with water for 300 g/times of ultrapure water 10 times, and concentrated until the conductivity of the aqueous phase became 3 μS/cm or less, thereby obtaining 361 g of the compound A10. As a result of FD-MS analysis of the obtained Compound A10, the number average molecular weight was 934.

Hereinafter, a synthesis example of the (meth)acrylic acid derivatives (B1 to B3) used in the above synthesis examples will be described.

[Synthesis of Compound B1]

In a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube, 420 g (4.2 mol) of succinic anhydride and 656 g (5.0 mol) of 2-hydroxyethyl methyl methacrylate were mixed with phenothiazine as a polymerization inhibitor. The azine was 0.05 g, and the mixture was heated to 110 ° C to cause a reaction for 5 hours. The reaction product was diluted with 2,500 g of toluene, washed with water of 800 g of ultrapure water for 6 times, and concentrated to obtain 850 g of Compound B1. As a result of HPLC and NMR analysis of the obtained Compound B1, it was confirmed that the desired product B1 of 2-hydroxyethyl methacrylate and succinic anhydride was obtained.

[Synthesis of Compound B2]

480 g (4.8 mol) of succinic anhydride, 577 g (4 mol) of 4-hydroxybutyl acrylate, and phenothiazine as a polymerization inhibitor were mixed in a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube. And add The reaction was allowed to proceed for 5 hours at a temperature of 110 ° C. The reaction product was diluted with 2000 g of toluene, washed with water of 1000 g of ultrapure water for 5 times, and concentrated to obtain 920 g of compound B2. As a result of HPLC and NMR analysis of the obtained compound B2, it was confirmed that the desired reaction product B2 of methyl 4-hydroxybutyl acrylate and succinic anhydride was obtained.

[Synthesis of Compound B3]

In a 2000 ml four-necked flask equipped with a stirrer, an air guide tube, a thermometer, and a cooling tube, 120 g (1.2 mol) of succinic anhydride and 472 g (1.0 mol) of 6-Hexanolide 3 molar add-on of purified 2-hydroxyethelmethacrylate were mixed as a polymerization inhibitor. Phenothiazine 0.05 g, and allowed to react to 110 ° C for 5 hours. Refined 2-hydroxyethyl methacrylate 6-caprolactone addenda 3 molar addenda is a commercially available 2-hydroxyethyl methacrylate 6-caprolactone addenda 3 molar addition Column purification product of the product (PLACCEL FM3 Daicel Chemical Industry Co., Ltd.).

The reaction product was diluted with 2000 g of toluene, washed with water of 1000 g of ultrapure water 10 times, and concentrated to obtain 584 g of compound B3. As a result of HPLC and NMR analysis of the obtained compound B3, it was confirmed that the reaction product B3 of the desired caprolactone 3 molar modified methacrylate and succinic anhydride was obtained.

(b) Thermal latent hardener

As the thermal latent curing agent, (i) 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH-J Ajinomoto FINETECHNO Co., Ltd.) is appropriately selected, (ii) Dioxodioic acid (ADH, manufactured by Japan FINECHEM Co., Ltd.).

(c) Free radical polymerization initiator

As the radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by CIBA SPECIALTY CHEMICAL Co., Ltd.) which functions as a photoradical polymerization initiator is used.

(d) filler

As the filler, spherical cerium oxide (primary average particle diameter: 0.7 μM) (manufactured by Admafine A-802 ADMATIC Co., Ltd.) was used.

(e) Epoxy resin

As the epoxy resin, an o-cresol novolac type solid epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was used.

(f) Acrylic compound

As the component (f), (i) dimethacrylate (epoxy ester 3000M, manufactured by Kyoeisha Chemical Co., Ltd.) of bisphenol A type resin is diluted with (i) using toluene and ultrapure water, and by The compound obtained by repeating the washing for 12 times and performing the high-purification treatment, and (ii) diluting the bisphenol A and the EO add-on diacrylate (Biscoat #700 Osaka Organic Chemical Industry Co., Ltd.) using toluene and ultrapure water, Further, it was used by repeating the washing for 12 times to obtain a compound obtained by high-purification treatment.

(g) Other additives

As other additives, γ-glycidoxy trimethoxy silane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), which is commercially available as a decane coupling agent, was used.

Further, in each of the examples and the comparative examples, the following were measured and evaluated to evaluate the characteristics of the liquid crystal sealing agent. The above items include: LCD The viscosity stability of the sealant, the adhesion strength of the liquid crystal sealing agent, and the display property of the liquid crystal display panel. The details of each measurement are shown below. The adhesive strength of the liquid crystal sealing agent was evaluated by measuring (1) the bonding strength of the liquid and light-curable liquid crystal sealing agent, and (2) the bonding strength of the thermosetting liquid crystal sealing agent. Further, the display property of the liquid crystal display panel is a sample measurement (1) a liquid crystal display panel produced in a general manner, (2) a display property of a liquid crystal display panel with a light-shielding region added thereto, and (3) a liquid crystal display panel produced only by thermal curing. The three types of displayability are evaluated.

[Viscosity stability of liquid crystal sealant]

The viscosity of the liquid crystal sealant at 25 ° C was measured using an E-type viscometer. At the time of viscosity measurement, 100 parts by mass of the liquid crystal sealing agent was placed in a polyethylene container, and after sealing, it was stored at 25 ° C for 5 days. Next, after a predetermined period of time, the viscosity value at 25 ° C was measured with an E-type viscometer. Then, using the measured value, the rate of change of the viscosity value after the passage of 25 ° C / 5 days when the viscosity value before sealing was 100 was calculated. In this case, when the change rate is 20% or less, the viscosity stability is high and is good (○), and when the change is more than 20%, the viscosity stability is low and the defect is poor (×), and the liquid crystal sealant is evaluated in two grades. Viscosity stability.

[Adhesive strength of liquid crystal sealant]

1. Bonding strength of liquid and heat-hardened liquid crystal sealant

First, a liquid crystal sealing agent to which 1 mass% of 5 μm glass fiber was added was screen-printed on an alkali-free glass of 25 mm × 45 mm × 5 mm thick to form a circular shape having a diameter of 1 mm. Then, the same glass which was paired with the substrate was bonded to each other by a cross, and then fixed by a jig, and an ultraviolet ray irradiation apparatus (manufactured by USHIO Electric Co., Ltd.) was used to irradiate ultraviolet rays of 100 mW/cm ² to cure the liquid crystal sealing agent. At this time, the irradiation energy of ultraviolet rays was 2000 mJ.

A test piece which hardened the liquid crystal sealing agent by light was heat-treated at 120 ° C for 60 minutes in an oven to prepare a test piece. Using a tensile tester (Model 210, manufactured by INTESCO Co., Ltd.), the tensile speed was 2 mm/min, and the prepared test piece was peeled off in a direction parallel to the bottom surface of the glass, and the plane tensile strength of the completed test piece was measured. Among them, the bonding strength was evaluated in two levels according to the magnitude of the plane tensile strength. In other words, when the tensile strength is 10 MPa or more, the adhesive strength is good (○), and when the tensile strength is less than 10 MPa, the adhesive strength is low and the hardness is (×).

2. Bond strength of thermosetting liquid crystal sealant

First, a liquid crystal sealing agent to which 1 mass% of 5 μm glass fiber was added was screen-printed on an alkali-free glass of 25 mm × 45 mm × 5 mm thick to form a circle having a diameter of 1 mm, and the pair of identical glass was cross-shaped. fit. Next, the two substrates which were bonded together were heat-treated at 120 ° C for 60 minutes in an oven, and the liquid crystal sealing agent was cured only by thermal curing to prepare a test piece.

The plane tensile strength of the prepared test piece was measured using a tensile tester (Model 210, manufactured by INTESCO Co., Ltd.). In this case, the measurement of the tensile strength of the plane and the evaluation of the measurement results are the same as those described in the above (A) bonding strength between the light-curable liquid crystal sealing agent.

[Displayability of Liquid Crystal Display Panel]

1. Displayability of a liquid crystal display panel fabricated by light and heat hardening

Liquid crystal sealing using 1 mass percent of 5 μm glass fiber A 35 mm × 40 mm frame having a line width of 0.5 mm and a thickness of 50 μm was drawn on a 40 mm × 45 mm glass substrate (manufactured by RT-DM88 PINEHC Co., Ltd.) having a transparent electrode and an alignment film. The drawing is performed using a dispenser (SHOTMASTER, Musashi ENGINEERING).

Next, a liquid crystal material (MLC-11900-000, manufactured by MERCK Co., Ltd.) corresponding to the panel content after the substrates are bonded to each other is precisely dispensed with a dispenser on the glass substrate which is paired with the substrate on which the seal pattern is formed. Then, the two glass substrates were superposed under a reduced pressure of 90 Pa to block the liquid crystal, and then ultraviolet rays of 100 mW/cm ² were irradiated with an ultraviolet irradiation device (manufactured by USHIO Electric Co., Ltd.) to cure the liquid crystal sealing agent. At this time, the irradiation energy of ultraviolet rays was 2000 mJ. The source uses a metal halide lamp. An ultraviolet cumulative light meter (UVR-T35 TOPCON) having a measurement wavelength range of 300 to 390 nm and a peak sensitivity wavelength of 365 nm was used for the measurement of the integrated light amount. After the liquid crystal sealing agent was cured by light, it was further heated at 120 ° C for 60 minutes, and the liquid crystal sealing agent was cured by heat treatment.

A polarizing film is attached to both surfaces of the two bonded substrates as a liquid crystal display panel. A voltage of 5 V was applied to the liquid crystal display panel using a DC power supply device to drive the liquid crystal display panel. At this time, it is visually observed whether or not the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealing agent functions normally from the initial stage of driving, and the display property of the liquid crystal display panel is evaluated in two levels based on a predetermined standard. Here, the case where the liquid crystal display panel is always in the liquid crystal display function until the sealing is performed is regarded as good displayability (○); the display function is not displayed when the display function is not displayed from the vicinity of the sealing time until the inner side of the frame is deviated by 0.3 mm. Very poor (×).

2. Displayability of liquid crystal display panel with additional shading area

Using a liquid crystal sealing agent to which 1 mass% of 5 μm glass fiber was added, a 35 mm × 45 mm glass substrate (manufactured by RT-DM88 PINEHC) having a transparent electrode and an alignment film was used to draw 35 mm of a line width of 0.5 mm and a thickness of 50 μm. × 40mm frame. The drawing is performed using a dispenser (SHOTMASTER, Musashi ENGINEERING).

Next, a liquid crystal material (MLC-11900-000, manufactured by MERCK Co., Ltd.) corresponding to the amount of the panel after bonding was precisely dispensed using a dispenser. Next, after the two glass substrates were superposed under a reduced pressure of 90 Pa, a load was applied, and the sealing portion of the front substrate was covered with an aluminum foil tape to avoid direct irradiation with ultraviolet rays. Then, a liquid crystal display panel in which a light-shielding region is added by light or heat-hardening the liquid crystal sealing agent is produced by the same method as the measurement method of the liquid crystal display panel described above.

The display function of the completed liquid crystal display panel was measured and evaluated in the same manner as in the above-mentioned "1. Displayability of liquid crystal display panel produced by light and heat hardening". However, the criteria for evaluating the display performance of the liquid crystal display panel are the same as those described above, and thus detailed descriptions thereof will be omitted.

3. Displayability of liquid crystal display panel made only by thermal hardening

Using a liquid crystal sealing agent to which 1 mass% of 5 μm glass fiber was added, a 35 mm × 45 mm glass substrate (manufactured by RT-DM88 PINEHC) having a transparent electrode and an alignment film was used to draw 35 mm of a line width of 0.5 mm and a thickness of 50 μm. × 40mm frame. The drawing is performed using a dispenser (SHOTMASTER, Musashi ENGINEERING).

Next, using the dispenser to precisely inject the equivalent of the panel after the bonding A liquid crystal material of a content amount (MLC-11900-000, manufactured by MERCK Co., Ltd.). Next, the two glass substrates were superposed under a reduced pressure of 90 Pa, and then heat-treated at 120 ° C for 60 minutes in an oven to cure the liquid crystal sealing agent.

A polarizing film is attached to both surfaces of the two bonded substrates as a liquid crystal display panel. A voltage of 5 V was applied to the liquid crystal display panel using a DC power supply device to drive the liquid crystal display panel. At this time, it is visually observed whether or not the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealing agent functions normally from the initial stage of driving, and the display property of the liquid crystal display panel is evaluated in two levels based on a predetermined standard. However, the criteria for evaluating the display performance of the liquid crystal display panel are the same as those of the above-described method, and thus the description thereof is omitted.

[Example 1]

As the component (e), 5 parts by mass of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in 10 parts by mass of a highly pure epoxy group (3000 M, In the Gongrongsha Chemical Co., Ltd., it is prepared into a homogeneous solution. After the solution was cooled, 52 parts by mass of the component (a): Compound A1 was added as the component (c): 1-hydroxycyclohexyl phenyl ketone which functions as a photoradical polymerization initiator (IRGACURE 184, CIBA SPECIALTY CHEMICAL) (manufactured by the company) 2 parts by mass, as component (b): 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH-J Ajinomoto FINETECHNO) 10 parts by mass, as component (d): 20 parts by mass of spherical cerium oxide (manufactured by Admafine A-802 ADMATIC Co., Ltd.) as component (g): γ-glycidoxypropyltrimethoxydecane (KBM403 Shin-Etsu Chemical Co., Ltd.) Industrial (stock) system 1 part by mass, premixed using a mixer. Mixing with a three-roller mixer until solid The raw material was 5 μm or less, and was filtered with a filter having a mesh opening of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.). The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P1).

[Embodiment 2]

A liquid crystal sealing agent (P2) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A2 was used instead of the compound A1 as the component (a).

[Example 3]

A liquid crystal sealing agent (P3) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A3 was used instead of the compound A1 as the component (a).

[Example 4]

A liquid crystal sealing agent (P4) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A4 was used instead of the compound A1 as the component (a).

[Example 5]

As the component (e), 5 parts by mass of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in 24 parts by mass of a highly purified epoxy ester (3000 M, In the Gongrongsha Chemical Co., Ltd., it is prepared into a homogeneous solution. After the solution was cooled, 20 parts by mass of the component (a): Compound A2 was added as the component (c): 1-hydroxycyclohexyl phenyl ketone which functions as a photoradical initiator (IRGACURE 184, CIBA SPECIALTY CHEMICAL ( 5 parts by mass, as component (b): 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH-J) 15 parts by mass of ajinomoto FINETECHNO Co., Ltd. as component (d): 30 parts by mass of spherical cerium oxide (Admafine A-802 ADMATIC), and (g) other additives: γ-glycidyloxy 1 part by mass of propyltrimethoxydecane (manufactured by KBM403 Shin-Etsu Chemical Co., Ltd.), and premixed using a mixer. Further, the mixture was kneaded by a three-roller kneader until the solid raw material was 5 μm or less, and the mixture was filtered with a filter having a mesh opening of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.). The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P5).

[Embodiment 6]

6 parts by mass of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was dissolved and dissolved in 6 parts by mass of a highly purified epoxy ester (3000 M, as the component (e). In the Gongrongsha Chemical Co., Ltd., it is prepared into a homogeneous solution. After the solution was cooled, 9 parts by mass of the compound (a) and 26 parts by mass of the compound A5 and 26 parts by mass of the compound A6 were added as the component (c): 1-hydroxy group which functions as a photoradical polymerization initiator. 2 parts by mass of cyclohexyl phenyl ketone (IRGACURE 184, manufactured by CIBA SPECIALTY CHEMICAL Co., Ltd.) as component (b): 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin ( 10 parts by mass of AMICURE VDH-J Ajinomoto FINETECHNO Co., Ltd. as component (d): 14 parts by mass of spherical cerium oxide (Admafine A-802 ADMATIC), and as component (g): γ-shrinkage 1 part by mass of glyceryloxypropyltrimethoxydecane (manufactured by KBM403 Shin-Etsu Chemical Co., Ltd.), and premixed using a mixer. The mixture was further kneaded by a three-roller kneader until the solid raw material was 5 μm or less, and a filter having a mesh opening of 10 μm (MSP-10-E10S, The mixture is filtered by ADVANTEC. The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P6).

[Embodiment 7]

As component (a): 81 parts by mass of compound A2, as component (b): 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH-J Ajinomoto FINETECHNO 10 parts by mass of (d) component: 8 parts by mass of spherical cerium oxide (Admafine A-802 ADMATIC), and as component (g): γ-glycidoxypropyltrimethoxy 1 part by mass of decane (KBM403 Shin-Etsu Chemical Co., Ltd.) was premixed using a mixer. Further, the mixture was kneaded by a three-roller kneader until the solid raw material was 5 μm or less, and the mixture was filtered with a filter having a mesh opening of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.). The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P7).

[Embodiment 8]

As the component (e), 5 parts by mass of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in the high-purity bisphenol A as the component (f). EO Additive Acrylate (Biscoat #700 Osaka Organic Chemical Industry ( In a system of 10 parts by mass, it was prepared into a homogeneous solution. After the solution was cooled, 52 parts by mass of the component (a): Compound A7 was added as the component (c): 1-hydroxycyclohexyl phenyl ketone which functions as a photoradical polymerization initiator (IRGACURE 184, CIBA SPECIALTY CHEMICAL) (part) system 2 parts by mass, as component (b): 10 parts by mass of AMICURE ADH (manufactured by FINECHEM Co., Ltd.), as component (d): spherical cerium oxide (Admafine A- 20 parts by mass of 802 ADMATIC, and 1 part by mass of (g) component: γ-glycidoxypropyltrimethoxydecane (KBM403, Shin-Etsu Chemical Co., Ltd.), premixed with a mixer Mixed. Further, the mixture was kneaded by a three-roller kneader until the solid raw material was 5 μm or less, and the mixture was filtered with a filter having a mesh opening of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.). The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P8).

[Embodiment 9]

A liquid crystal sealing agent (P9) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A8 was used instead of the compound A1 as the component (a).

[Embodiment 10]

A liquid crystal sealing agent (P10) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A9 was used instead of the compound A1 as the component (a).

[Example 11]

A liquid crystal sealing agent (P11) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A10 was used instead of the compound A1 as the component (a).

[Embodiment 12]

As the component (e), 15 parts by mass of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) was heated and dissolved in 22 parts by mass of high-purity bisphenol A and EO addenda. Diacrylate (Biscoat # V700 Osaka Organic Chemical Industry Co., Ltd.) was prepared into a homogeneous solution and then cooled again. After the solution is cooled, it is added as component (a): Compound A7 20 In the component (c): 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by CIBA SPECIALTY CHEMICAL Co., Ltd.) which functions as a photoradical polymerization initiator, as component (b): 15 parts by mass of diammonium adipate (AMICURE ADH, manufactured by FINECHEM Co., Ltd.), as component (d): 25 parts by mass of spherical cerium oxide (Admafine A-802 ADMATIC), and as component (g) : γ-glycidoxypropyltrimethoxydecane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part by mass, and premixed using a mixer. Further, the mixture was kneaded by a three-roller kneader until the solid raw material was 5 μm or less, and the mixture was filtered with a filter having a mesh opening of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.). The obtained filtrate was subjected to vacuum defoaming treatment to prepare a liquid crystal sealing agent (P12).

[Comparative Example 1]

A liquid crystal sealing agent (Q1) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A5 was used instead of the compound A1 as the component (a).

[Comparative Example 2]

A liquid crystal sealing agent (Q2) was prepared in the same manner as in Example 1 except that 52 parts by mass of the compound A6 was used instead of the compound A1 as the component (a).

[Comparative Example 3]

A liquid crystal sealing agent (Q3) was prepared in the same manner as in Example 1 except that the component (a) was used in an amount of 26 parts by mass of the compound A5 and 26 parts by mass of the compound A6 in place of the compound A1.

[Comparative Example 4]

A liquid crystal sealing agent (Q4) was prepared in the same manner as in Example 1 except that 62 parts by mass of the epoxy group 3000M was used instead of the compound A1 and the epoxy group 3000M used in Example 1 as the component (a). .

[Comparative Example 5]

A liquid crystal sealing agent (Q5) was prepared in the same manner as in Example 8 except that 52 parts by mass of the compound C1 synthesized by the following synthesis method was used instead of the compound A7.

[Synthesis of Compound C1]

A bisphenol A type epoxy resin (Epiclon 850RP manufactured by Dainippon Ink Chemical Co., Ltd.) was mixed in a 500-ml flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube. 175 g, methacrylic acid: 43 g, triethanolamine as a catalyst: 0.2 g, hydroxymonomethylether (0.2 g) as a polymerization inhibiting agent, and the mixture was heated and stirred at 110 ° C while blowing dry air on one side. Compound C1 was obtained in an hour. The compound C1 thus obtained was repeatedly subjected to a washing treatment for 12 times with ultrapure water. As a result of HPLC and NMR analysis of the compound C1, it was confirmed that 50% of the epoxy group contained therein was a bisphenol A type epoxy resin modified with a methacryl oxime group. As a result of FD-MS analysis of the obtained compound C1, the number average molecular weight was 426.

[Comparative Example 6]

A liquid crystal sealing agent (Q6) was prepared in the same manner as in Example 8 except that the component (a) was used in an amount of 52 parts by mass of the compound C2 synthesized by the following synthesis method.

[Synthesis of Compound C2]

A bisphenol A type epoxy resin was placed in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube: Epiclon (EPICLON) EXA850CRP manufactured by Dainippon Ink and Chemicals Co., Ltd.) 175 g, acrylic acid 37 g, triethanolamine as a catalyst: 0.2 g, hydroxymonomethylether as a polymerization inhibiting agent: 0.2 g, and then mixed. The mixture was heated while stirring at 110 ° C for 12 hours while blowing dry air to obtain a compound C2. The obtained compound C2 was repeatedly subjected to a washing treatment 12 times with ultrapure water. As a result of HPLC and NMR analysis of the compound C2, it was confirmed that 50% of the epoxy group contained was a bisphenol A type epoxy resin modified with an acrylonitrile group. As a result of FD-MS analysis of the obtained compound C2, the number average molecular weight was 412.

[Comparative Example 7]

A liquid crystal sealing agent (Q7) was prepared in the same manner as in Example 1 except that 26 parts by mass of the above compounds C1 and C2 were used instead of the compound A1.

[Comparative Example 8]

The same applies to Example 8 except that 52 parts by mass of an epoxy group of diacrylate as a bisphenol A type epoxy resin (3000 M, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the compound A7. A liquid crystal sealant (Q8) was prepared in the manner.

The evaluation results of the liquid crystal sealing agents obtained in Examples 1 to 12 and Comparative Examples 1 to 8 are summarized in Tables 1 to 2.

As shown in Table 1 and Table 2, in the liquid crystal sealing agent used in the liquid crystal sealing agent P1 to P12 of the present invention, the viscosity stability, the bonding strength, and the display property in the vicinity of the seal of the oxy display panel using the same, Good evaluation results were confirmed in each item of visibility in the vicinity of the seal of the light-shielding region. Further, when the liquid crystal sealing agent was only thermally cured, it was confirmed that the bonding strength was high and the display property of the liquid crystal display panel was excellent.

On the other hand, as shown in Comparative Examples 1 to 6, the liquid crystal sealing agent was confirmed as a compound having a (meth) acrylate group and an epoxy group, and a compound having a number average molecular weight of less than 500 was used as a raw material. The viscosity stability is low, and display unevenness occurs in the vicinity of the seal, so the display property is low, which is inferior to the respective embodiments. Further, as shown in Comparative Examples 4 and 8, it was confirmed that the liquid crystal sealing agent which is a raw material of a methacrylated epoxy resin which is different from the structure of the present invention has low viscosity stability and adhesive strength, and is remarkably inferior.

(industrial availability)

The liquid crystal sealing agent of the present invention has high viscosity stability and hardenability and is excellent. Therefore, the line width of the seal pattern is reduced, and the number of times the apparatus such as a dispenser is replaced with the liquid crystal sealant is less likely to be suppressed, and the yield can be improved and the hardening time of the liquid crystal display panel can be shortened and manufactured. In addition, the solubility of the liquid crystal sealing agent to the liquid crystal is suppressed to be low, and is also suitable for the liquid crystal dropping method.

Claims (9)

A liquid crystal sealing agent comprising: (a) a compound having a (meth)acrylonium group and a glycidyl group in the molecule and having a number average molecular weight of 500 to 2,000, wherein the component (a) has (i) a (meth)acrylonyl group and a glycidyl group compound obtained by reacting an epoxy compound having 3 or 4 glycidyl groups in the molecule with (ii) a (meth)acrylic acid derivative having a carboxyl group; (b) heat a latent hardening agent; (c) a radical polymerization initiator; and (d) a filler, wherein the component (a) is contained in an amount of 5 to 90 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent, 1 to 25 parts by mass of the component, and the component (c) is 0.01 to 5 parts by mass, and the component (d) is contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the liquid crystal sealing agent other than the filler. The liquid crystal sealing agent of claim 1, wherein the component (i) is represented by the following general formula (i-1), (i-2), (i-3) or (i-4) Compound [R ₇₁ in the above general formula (i-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms] [R ₇₁ in the above general formula (i-2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms] [In the above general formula (i-4), R ₈₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₈₂ represents a hydrogen atom or a methyl group]. The liquid crystal sealing agent of claim 1, wherein the component (ii) is acrylic acid, methacrylic acid, a compound represented by the following general formula (ii-1) or general formula (ii-2); [In the above general formula (ii-1), R ₉₁ represents a hydrogen atom or a methyl group, X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (t2), and X ₄₂ represents carbon 1 to 20 alkylene groups or 2 to 6 carbon atoms (alkenylene) [In the above general formula (t2), Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and O ₅₁ is bonded to an O group of the above-mentioned general formula (ii-1), n An integer representing 1 to 10] [In the above general formula (ii-2), R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group, X ₆₁ represents a group represented by the following general formula (t3), and X ₆₂ represents a carbon number of 1 to 10; An alkylene group, X ₆₃ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and i and j each independently represent an integer of 0 or 1. [In the above general formula (t3), Y ₇₁ and Y ₇₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and an O bond of a CO group with an acrylonitrile group in the above general formula (ii-2)]. The liquid crystal sealing agent of claim 1, which further comprises any one of (e) an epoxy resin or (f) an acrylic compound. The liquid crystal sealing agent of claim 1, wherein the component (c) is a photoradical polymerization initiator. For example, the liquid crystal sealing agent of claim 1 of the patent scope, wherein The component (c) is a thermal radical polymerization initiator. The liquid crystal sealing agent of claim 1, wherein the component (d) is an inorganic filler. A method for manufacturing a liquid crystal display panel, wherein a liquid crystal display panel is manufactured by bonding two substrates facing each other by a liquid crystal sealing agent, the method comprising: preparing a process of preparing one or more substrates, wherein the substrate has a pixel arrangement area a frame-shaped display region formed by encapsulating the liquid crystal sealing agent according to claim 1; a process of injecting liquid crystal into the display region in an unhardened state or another substrate; and the liquid crystal is dripped a process in which a substrate and another substrate are overlapped; and a process of irradiating light and heating the liquid crystal sealing agent sandwiched between the two substrates, or performing only one of irradiation light and heating. A liquid crystal display panel obtained by the method for manufacturing a liquid crystal display panel according to claim 8 of the patent application.