KR20110036112A - Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel - Google Patents

Abstract

The present invention relates to a liquid crystal sealing agent that can be applied to a liquid crystal display panel. The liquid crystal sealing agent of this invention has a (meth) acryloyl group and glycidyl group in (a) molecule | numerator, the number average molecular weights are 500-2000, the (b) heat | fever latent hardening | curing agent, (c) radical polymerization initiator, And (d) filler. Since the component (a) is a high molecular weight, high reactivity and latent curability, it has a low solubility, high curability and high viscosity stability to the liquid crystal. Therefore, when a liquid crystal display panel is manufactured using such a liquid crystal sealing agent, the adhesive strength of the board | substrate and the hardened | cured material of a liquid crystal sealing agent is high, and liquid crystal contamination is suppressed low, maintaining high productivity, and since display property is high and favorable, A high quality liquid crystal display panel can be manufactured.

Description

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

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

In recent years, with the development of broadband and the development of small electronic devices such as digital cameras and mobile phones, the demand for liquid crystal display panels (FPD) (Flat Panel Disp1ay) has become an exceptional extension in terms of thinness, light weight, and low power consumption. have. The liquid crystal display panel has a structure in which a liquid crystal is enclosed between two transparent substrates bonded by a liquid crystal sealing agent, by controlling the orientation of the liquid crystal by applying a voltage to the liquid crystal, thereby adjusting the modulation of light transmitted through the substrate. It is a device that displays an image.

Conventionally, a liquid crystal display panel has been mainly manufactured by the liquid crystal injection system which manufactures a liquid crystal display panel by inject | pouring a liquid crystal into the liquid crystal cell which has the injection hole arrange | positioned between two board | substrates, and sealing an injection hole (for example, patent document 1). Reference). However, as the demand for liquid crystal display panels increases, productivity improvement is strongly demanded in the manufacturing field of liquid crystal display panels. However, the liquid crystal injection method requires a long time to inject the liquid crystals and further cures the liquid crystal sealing agent. Low productivity has become a big problem for the reason that heat processing for several hours is required at the temperature of 120-150 degreeC at the time of making it.

Therefore, recently, the liquid crystal dropping method attracts attention as a manufacturing method of the liquid crystal display panel which replaces a liquid crystal injection system. With a liquid crystal dropping system, first, either of two board | substrates forms an edge-shaped sealing pattern with a liquid crystal sealing agent using a dispenser or screen printing; A small amount of liquid crystal is dropped in this frame or on the other substrate; In a high vacuum, two substrates are stacked while the liquid crystal sealing agent is uncured; It is a method of manufacturing a liquid crystal display panel by irradiating an ultraviolet-ray with respect to the liquid crystal sealing agent between two board | substrates, and temporarily hardening, and then after-curing the liquid crystal sealing agent by heating.

According to this liquid crystal dropping method, since the time which encloses a liquid crystal in a liquid crystal cell is short, and hardening of a liquid crystal sealing agent is carried out by using light and a heating press body together, the hardening time of a liquid crystal sealing agent is also shortened. Productivity is improved more. As a liquid crystal sealing agent used for such a liquid crystal dropping system, the light and thermosetting liquid crystal sealing agent are proposed (for example, refer patent document 2, 3).

However, in the liquid crystal dropping system, since the liquid crystal directly contacts the liquid crystal sealing agent in an uncured state, the component of the liquid crystal sealing agent is eluted to the liquid crystal and the liquid crystal is liable to be contaminated. When the liquid crystal is contaminated in this manner, the display of the liquid crystal display panel is significantly lowered, which is a big problem. In addition, contamination of the liquid crystal is caused even when an uncured portion remains in the cured product of the liquid crystal sealing agent. It is because the liquid-crystal sealing agent component of an uncured state elutes to a liquid crystal from an uncured part. If the uncured portion remains in the cured product of the liquid crystal sealing agent, not only the liquid crystal is contaminated, but also the adhesive strength between the substrate constituting the liquid crystal display panel and the cured product of the liquid crystal sealing agent is lowered, which may cause deterioration of the quality of the liquid crystal display panel. high. Therefore, from the viewpoint of preventing contamination of the liquid crystal and increasing the adhesive strength, the curing proceeds to every corner in a short time, so that the uncured portion of the cured product is suppressed very little and the curing property is high and the solubility in the liquid crystal is low. The proposal of the sealing agent is calculated | required.

Until now, as a liquid crystal sealing agent which improved adhesive strength, the liquid crystal sealing agent which uses the partially acrylated or methacrylic epoxy resin obtained by making bisphenol-A epoxy resin react with acrylic acid or methacrylic acid is proposed (for example, See Patent Document 4). Moreover, the liquid crystal sealing agent which can prevent the contamination of a liquid crystal, Comprising: The liquid crystal which contains the acrylate epoxy resin which has a (meth) acryl group and a hydroxyl group, and the number of the said (meth) acryl groups is larger than the number of the said hydroxyl groups A sealing agent is proposed (for example, refer patent document 5).

[Patent Documents]

(Patent Document 1) International Publication No. 2004/039885

(Patent Document 2) Japanese Patent Application Laid-Open No. 2001-133794

(Patent Document 3) Japanese Patent Application Laid-Open No. 2002-214626

(Patent Document 4) Japanese Patent No. 372179

(Patent Document 5) Japanese Patent Application Laid-Open No. 2005-195978

However, since the partially acrylated epoxy resin described in patent document 4 is low in sclerosis | hardenability and is a low molecular weight body, it is easy to pollute a liquid crystal because it has high solubility to a liquid crystal. Moreover, in the liquid crystal sealing agent, high viscosity stability in the vicinity of room temperature is considered important, and it is preferable that the viscosity stability is high. As a reason, if the viscosity of a liquid crystal sealing agent is stable without fluctuation at room temperature, it is easy to form the sealing pattern of a desired line width on a board | substrate, and the yield at the time of liquid crystal display panel manufacture can be improved. . On the other hand, since the said partial methacrylation epoxy resin is low in viscosity stability in the vicinity of room temperature, it is not preferable as a raw material of a liquid-crystal sealing agent.

Moreover, although the acrylated epoxy resin like that described in patent document 5 is high in viscosity stability, and good, on the other hand, since it is low in sclerosis | hardenability, an uncured part tends to remain in the hardened | cured material of a liquid-crystal sealing agent. Therefore, the contamination of a liquid crystal and the low adhesive strength of the hardened | cured material of a liquid crystal sealing agent, and the board | substrate which comprises a liquid crystal display panel are problematic.

Therefore, a 1st object of this invention is to provide the liquid crystal sealing agent which was high in sclerosis | hardenability, the solubility with respect to liquid crystal is suppressed low, and high viscosity stability was maintained. Moreover, by using the liquid crystal sealing agent of this invention, contamination of a liquid crystal is prevented and the high productivity of the liquid crystal display panel with the adhesive strength of the hardened | cured material of such a liquid crystal sealing agent and the board | substrate which comprises a liquid crystal display panel maintains high productivity. It is a second object to provide a method which can be manufactured while.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject can be solved by paying attention to the molecular weight of the compound used as a raw material of a liquid-crystal sealing agent, and using the compound high molecular weight in the predetermined range. The invention has been completed.

That is, the said subject is solved by the liquid crystal sealing agent of this invention.

[1] (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 thermal latent curing agent, (c) a radical polymerization initiator, and (d) a filler Liquid crystal sealing agent comprising a.

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

[Formula I]

In the above formula (I),

R ₁₁ to R ₁₆ each independently represent a hydrogen atom or a methyl group, provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are not methyl groups;

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);

X ₁₃ and X _{14 each} represent a group having 1 to 10 carbon atoms and a group represented by the general formula (I-2);

A represents a group represented by the formula (I-3a), (I-3b) or (I-3c);

P each 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, m represents an integer of 0 to 4, where a + b + c + d + m = 6 , And a, b and c are not simultaneously zero;

j is an integer of 0 or 1, k and l represent the integer of 0-10, respectively.

(I-1)

In the above formula (I-1),

Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₂₁ is bonded to O of the acryloyl group of the formula (I),

n represents the integer of 1-10.

[Formula I-2]

In the above formula (I-2),

Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₃₂ is bonded to O of the acryloyl group of the formula (I).

[Formula I-3a]

In the above 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,

Z represents a single bond, -O- group, -S- group, -SO ₂ -group, -C (R ₄₃ ) (R ₄₄ )-group or a group represented by the following formula t1, wherein R ₄₃ and R ₄₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group,

r and s respectively independently represent the integer of 0-4.

[Formula t1]

[Formula I-3b]

In the above 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.

[Formula I-3c]

In the above 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] or [2], wherein the general formula (I) is at least one compound having at least one acryloyl group, methacryloyl group, and epoxy group in the molecule.

(4) The (meth) acryloyl group obtained by making (a) component react with the (meth) acrylic acid derivative which has 3 or 4 glycidyl groups in this molecule, and (ii) carboxyl group, and The liquid crystal sealing agent in any one of [1]-[3] which is a compound which has a glycidyl group.

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

[Formula VII-1]

R ₇₁ in Formula (X-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[Formula VII-2]

R ₇₁ in Formula (X-2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[Formula VII-3]

[Formula VII-4]

In the above formula (VII-4),

R ₈₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

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, formula (ii-1) or formula (ii-2).

[Formula ii-1]

In the 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,

X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms.

[Formula t2]

In the above formula t2,

Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₅₁ represents acryloyl group represented by Chemical Formula ii-1,

n represents the integer of 1-10.

[Formula ii-2]

In the 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 formula t3, X ₆₂ represents an alkylene group having 1 to 10 carbon atoms,

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.

[Formula t3]

In the above formula t3,

Y ₇₁ and Y ₇₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

The CO group is bonded to O of the acryloyl group of the 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.

[8] The liquid crystal sealing agent according to any one of [1] to [7], wherein the component (c) is an optical radical polymerization initiator.

[9] The liquid crystal sealing agent according to any one of [1] to [7], 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 amount of the component (a) is 5 to 90 parts by mass based on 100 parts by mass of the liquid crystal sealing agent.

Moreover, the said subject is solved by the manufacturing method of the liquid crystal display panel of this invention, and the liquid crystal display panel obtained by this.

[11] The method for manufacturing a liquid crystal display panel produced by bonding two opposed substrates together through a liquid crystal sealing agent, wherein the pixel array region is formed by the liquid crystal sealing agent according to any one of [1] to [10]. A step of preparing one or more substrates having an edge-shaped display area formed to be surrounded; a step of dropping a liquid crystal onto the other substrate or in the display area in an uncured state; and the other side of the substrate on which the liquid crystal is dropped And a step of stacking the substrates, and applying either light and heat, or light or heat to the liquid crystal sealing agent sandwiched between the two substrates.

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

ADVANTAGE OF THE INVENTION According to this invention, in addition to high viscosity stability and sclerosis | hardenability, the liquid crystal sealing agent which can provide the high adhesive strength of the hardened | cured material of a liquid crystal sealing agent, and the board | substrate which comprises a liquid crystal display panel, and also can prevent contamination of a liquid crystal. Can be provided. Moreover, by using the liquid crystal sealing agent of this invention, the manufacturing method of the liquid crystal display panel which can obtain a high quality liquid crystal display panel, maintaining high productivity can be provided.

Next, the present invention will be described in detail. The liquid-crystal sealing agent of this invention contains a (meth) acryloyl group and glycidyl group in (a) molecule | numerator, the number average molecular weights are 500-2000, the (b) heat | fever latent hardening | curing agent, (c) radical polymerization It is characterized by including an initiator and (d) filler. Each component used for the liquid crystal sealing agent of this invention is demonstrated below.

[Compound which has (meth) acryloyl group and glycidyl group in (a) molecule, and number average molecular weight is 500-2000]

The compound (also called "(a) component") which has a (meth) acryloyl group and glycidyl group in the (a) molecule of this invention, and has a number average molecular weight 500-2000 is also acryloyl group or methacryl in a molecule | numerator. A compound containing a royl group and glycidyl group, and optimized in the range whose number average molecular weights are 500-2000 is said. The number average molecular weight can be measured based on polystyrene as a standard by gel permeation chromatography (GPC).

As mentioned above, since the (a) component of this invention contains the (meth) acryloyl group which shows latent sclerosis | hardenability, it is high in viscosity stability also in low temperature area | regions like room temperature vicinity. On the other hand, since it has a highly reactive glycidyl group in a molecule | numerator, when (a) component is used as a raw material of a liquid crystal sealing agent, sclerosis | hardenability is high and a favorable liquid crystal sealing agent can be obtained. Such a liquid-crystal sealing agent has high storage stability and applicability | paintability to a board | substrate, and hardening progresses to every corner in a short time also in the place like a light shielding area | region. As a result, the contamination of a liquid crystal is prevented, and the adhesive strength of the hardened | cured material of a liquid crystal sealing agent and a board | substrate is high, and a liquid crystal display panel with favorable display property can be manufactured, maintaining high productivity.

In addition, the number average molecular weight of (a) component of this invention is adjusted in the range of 500-2000. Therefore, it has the characteristic that the solubility to liquid crystal is suppressed low. Generally, although a high molecular weight compound tends to become high in viscosity, if a number average molecular weight is adjusted in the said range, the liquid crystal sealing agent of low viscosity can be obtained, suppressing liquid-crystal contamination. Moreover, it is preferable that the number average molecular weights of (a) component are 800-1800 from a viewpoint of making solubility with respect to a liquid crystal low, and making it low viscosity.

From the viewpoint of achieving both the improvement of the curability of the liquid crystal sealing agent and the deterioration of the liquid crystal contamination, as the first component (a), at least one compound having at least one acryloyl group, methacryloyl group and an epoxy group together in a molecule thereof. Is preferably. The more the number of containing epoxy groups etc. with high reactivity, the hardenability of such a compound improves. In addition, the higher the molecular weight of the compound capable of being the component (a), the more the liquid crystal contamination is prevented.

When using (a) component as a raw material of a liquid crystal sealing agent, it is preferable to set it as 5-90 mass parts with respect to 100 mass parts of liquid crystal sealing agents, and, as for the usage-amount of (a) component, it is more preferable to set it as 20-60 mass parts. Do. Thereby, while the characteristic of (a) component mentioned above is reflected preferably as a characteristic of a liquid-crystal sealing agent, the adhesive strength of the hardened | cured material of a liquid-crystal sealing agent and the board | substrate which comprises a liquid crystal display panel becomes high, and display is favorable. A liquid crystal display panel excellent in the property can be obtained.

[1st (a) component]

As (a) component of this invention, it is preferable that it is a compound (it is also called "1st (a) component") represented by following General formula (I).

(I)

In the above formula (I),

R ₁₁ to R ₁₆ each independently represent a hydrogen atom or a methyl group,

Provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are not methyl groups;

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);

X ₁₃ and X _{14 each} represent a group having 1 to 10 carbon atoms and a group represented by the general formula (I-2);

A represents a group represented by the formula (I-3a), (I-3b) or (I-3c);

P each 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 the integer of 0-3, d represents the integer of 1-3, m represents the integer of 0-4, where a + b + c + d + m = 6, and a , b and c are not simultaneously zero;

j is an integer of 0 or 1, k and l represent the integer of 0-10, respectively.

[Formula I-1]

In the above formula (I-1),

Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₂₁ is bonded to O of the acryloyl group of the formula (I),

n represents the integer of 1-10.

[Formula I-2]

In the above formula (I-2),

Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₃₂ is bonded to O of the acryloyl group of the formula (I).

[Formula I-3a]

In the above 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,

Z represents a single bond, -O- group, -S- group, -SO ₂ -group, -C (R ₄₃ ) (R ₄₄ )-group or a group represented by the following formula t1, wherein R ₄₃ and R ₄₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group,

r and s respectively independently represent the integer of 0-4.

[Formula t1]

[Formula I-3b]

In the above 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.

[Formula I-3c]

In the above 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 represented by Formula (I) reacts (ii) hydroxyl-group-containing (meth) acrylate with (benzene) benzene dicarboxylic anhydride or benzene tetracarboxylic anhydride, produces | generates a carboxylic acid ester group and a carboxyl group, (iii) said Synthesis is possible by binding a polyvalent glycidyl ether to the carboxyl group produced by the reaction.

Examples of the benzenedicarboxylic acid anhydride, benzenetetracarboxylic dianhydride or benzenetricarboxylic acid anhydride include phthalic anhydride, dodecenyl phthalic anhydride, octenyl phthalic anhydride, and 1,2,4,5-benzenetetracarboxylic dianhydride. Included. These compounds can also be used individually or in combination of multiple types.

In the example of said (ii) hydroxyl group containing (meth) acrylate, hydroxyalkyl (C2-C6) (meth) acrylate and polyalkylene (C2-C6) glycol mono (meth) acrylate Glycerol mono (meth) acrylate, glycerol diacrylate, glycerol acrylate methacrylate, pentaerythritol tri (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate; Or these lactone (C4-8) modified or alkylene (C2-6) oxide modified compounds. These compounds can also be used individually or in combination of multiple types.

Examples of the above (iv) polyvalent glycidyl ether include phenol novolac-type glycidyl ethers, biphenyl novolac-type glycidyl ethers, cresol novolac-type glycidyl ethers, and bisphenol A. Glycidyl ethers of the bisphenol type, glycidyl ethers of the bisphenol F type, glycidyl ethers of the bisphenol F type, glycidyl ethers of the diphenyl ether type, glycidyl ethers of the sulfide type, and oxysulfide Glycidyl ethers of fluorene type, glycidyl ethers of fluorene type, glycidyl ethers of adamantyl type, glycidyl ethers of resorcinol type, glycidyl ethers of catechol type, hydroquinone type Glycidyl ethers are included. These compounds can also be used individually or in combination of multiple types.

The compound represented by the formula (I) is essential to include an acryloyl group or methacryloyl group, and glycidyl group in the molecule.

In reaction which couple | bonds polyhydric glycidyl ether to the reaction product of benzene dicarboxylic acid anhydride or benzene tetracarboxylic acid anhydride, and a hydroxyl group containing (meth) acrylate, reaction temperature is 40-180 degreeC from a viewpoint of promoting reaction. It is preferable to make it substantially constant within the range of, and it is more preferable to set it as 50-130 degreeC. The said reaction temperature means the temperature in the reaction mixture which mixed various raw materials of 1st (a) component. The temperature in the reaction mixture can be easily measured by using a thermometer or the like.

In the reaction for binding polyhydric glycidyl ether, it is preferable to use a catalyst from the viewpoint of reaction promotion. Preferable examples of the catalyst used herein include organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organophosphorus salt compounds, imidazole compounds, and organometallic compounds.

Examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compounds include triethylamine and triethanolamine. Examples of the quaternary ammonium salt compound include trimethylammonium chloride and triethylbenzylammonium chloride. Examples of the organophosphorus compound include tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. 2-methylimidazole is contained in the example of the said imidazole compound. In addition, cobalt octenate is contained in the example of the said organometallic compound.

It is preferable that the usage-amount of the said catalyst is sufficient amount to accelerate reaction. Specifically, it is preferable to make the usage-amount of a catalyst into 0.01-5.0 mass% with respect to the total mass of a reaction mixture.

A polymerization inhibitor can also be put into the said reaction mixture as needed. A polymerization inhibitor means the compound which suppresses or stops advancing of the polymerization reaction in a reaction mixture. A polymerization inhibitor is not specifically limited, A well-known compound can be selected suitably and can be used. Preferred examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, phenothiazine, p-t-butylcatechol, p-benzoquinone and naphthoquinone. These compounds can also be used individually or in combination of multiple types.

In addition, an organic solvent may be added to the reaction mixture. Examples of preferred organic solvents include aromatic solvents such as toluene and xylene; Ketone solvents such as cyclohexanone; Although glycol type solvents, such as a propylene glycol monomethyl ether, are contained, it is not specifically limited. These organic solvents may be used alone or in combination of two or more.

[2nd (a) component]

Preferred examples of component (a) of the present invention include (meth) acrylic acid derivatives having an epoxy compound having three or four glycidyl groups and (ii) a carboxyl group in the molecule other than the first component (a). And (meth) acryloyl group obtained by making it react, and the compound (it calls also "the 2nd (a) component") which have glycidyl group are contained.

The method of manufacturing the 2nd (a) component of this invention is not specifically limited, For example, the method of making one or two glycidyl groups in the glycidyl group in (i) component, and the carboxyl group in (ii) component react Can be mentioned.

Although the said (i) component used as a raw material of 2nd (a) component may be a compound which has 3 or 4 glycidyl groups in a molecule | numerator, it will not specifically limit, Although (a) component preferable as a raw material of a liquid-crystal sealing agent In order to obtain, the compound whose molecular weight of (i) component is 400-800 is preferable. Preferable examples of the (i) component having such a molecular weight include the compounds represented by the following formula (X-1), (X-2), (X-3) or (X-4).

[Formula VII-1]

R ₇₁ in Formula (X-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[Formula VII-2]

R ₇₁ in Formula (X-2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[Formula VII-3]

[Formula VII-4]

In the above formula (VII-4),

R ₈₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R ₈₂ represents a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ₇₁ and R ₈₁ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group and a t-butyl group , Pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl groups. Especially, it is preferable that they are a hydrogen atom, a methyl group, and an ethyl group, and it is more preferable that they are a hydrogen atom.

Either a commercial item or a synthetic product may be sufficient as the trifunctional epoxy compound represented by the said Formula (VII-1), and the tetrafunctional epoxy compound represented by the said Formula (X-2). When synthesize | combining such an epoxy compound, the synthesis | combining method is not specifically limited. When synthesize | combining these compounds, it can synthesize | combine epihalohydrin according to a well-known epoxidation reaction, for example to the nucleus or tetranuclear body of the novolak-type compound obtained by condensation reaction of a phenol derivative and formalin. have. In addition, the example of the said well-known epoxidation reaction includes the method known as an industrial manufacturing method of the existing epoxy compound which can be obtained as an industrial raw material.

In addition, the compound represented by the said Formula (VII-3) and Formula (-4) is not specifically limited, either a commercial item or a synthetic product may be sufficient.

(Ii) Component of this invention is a viewpoint which makes high reactivity of the liquid crystal sealing agent and high viscosity stability compatible, when the high molecular weight of the said (a) component and said (a) component are used as a raw material of a liquid crystal sealing agent It is preferable that it is a compound represented by acrylic acid, methacrylic acid, and the following general formula (ii-1) or (ii-2).

[Formula ii-1]

In the 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,

X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms that are preferable as X ₄₁ in Formula (ii-1) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclopentylene group, and a hexamethylene group , Cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group are included. Especially, it is preferable that X <_41> is group represented by a C2-C6 alkylene group or the said general formula (t2).

Examples of the alkylene group having 1 to 20 carbon atoms that are preferable as X ₄₂ in the formula (ii-1) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclopentylene group, and a hexamethylene group , Cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group and octadecamethylene group are included.

Examples of the alkenylene group having 2 to 6 carbon atoms which is preferable as X ₄₂ in the formula (ii-1) include a -CH = CH- group, -CH = CH-CH ₂ -group, and -CH = CH-CH ₂ -CH _2- . Groups, —CH ₂ —CH═CH—CH ₂ — groups are included. Especially, as X <_42> , a C1-C6 alkylene group, such as a methylene group, an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group, and -CH = CH- group are preferable, and a methylene group It is more preferable that they are a C1-C4 alkylene group, such as an ethylene group, trimethylene group, and tetramethylene group, and -CH = CH- group.

[Formula t2]

In the above formula t2,

Y ₅₁ and Y ₅₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

Y ₅₁ is bonded to O of the acryloyl group represented by Formula ii-1,

n represents the integer of 1-10.

Examples of the alkylene group having 1 to 10 carbon atoms that are preferable as Y ₅₁ and Y ₅₂ in the general formula t2 include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclopentylene group, and hexamethylene Group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group are included. Especially, a C2-C6 alkylene group is preferable. In addition, n in the said general formula t2 shows the integer of 1-10, More preferably, it is an integer of 1-6.

[Formula ii-2]

In the 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 formula t3, X ₆₂ represents an alkylene group having 1 to 10 carbon atoms,

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.

[Formula t3]

In the above formula t3,

Y ₇₁ and Y ₇₂ each independently represent an alkylene group having 1 to 10 carbon atoms,

The CO group is bonded to O of the acryloyl group of the formula (ii-2).

Examples of the alkylene group having 1 to 10 carbon atoms that are preferable as R ₆₁ and R ₆₂ in the formula (ii-2) include methylene group, ethylene group, methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, cyclopentylene group, Hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group are included.

Examples of the alkylene group having 1 to 20 carbon atoms that are preferable as X ₆₃ in Formula (ii-2) include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a cyclopentylene group, and a hexamethylene group , Cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, nonamethylene group, dodecamethylene group, pentadecamethylene group, hexadecamethylene group and octadecamethylene group are included.

Examples of the alkenylene group having 2 to 6 carbon atoms which are preferable as X ₆₃ in the formula (ii-2) include a -CH = CH- group, a -CH = CH-CH ₂ -group, and -CH = CH-CH ₂ -CH _2- . Groups and —CH ₂ —CH═CH—CH ₂ — groups. In addition, X ₅₃ is preferably 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, a hexamethylene group, and a -CH = CH- group, and a methylene group, It is more preferable that they are C1-C4 alkylene groups, such as an ethylene group, trimethylene group, and a tetramethylene group, and -CH = CH- group.

Y ₇₁ and Y ₇₂ in Formula (t3) correspond to X ₆₁ . Examples of alkylene groups preferred as Y ₇₁ and Y ₇₂ include methylene group, ethylene group, methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene Groups, octamethylene groups, nonamethylene groups and decamethylene groups are included. Especially, as an alkylene group, it is more preferable that it is a C2-C6 alkylene group.

[Method for Producing Compound Represented by Formula (II-1)]

Although the compound represented by the said Formula (ii-1) may be industrially manufactured, "(meth) acrylic acid derivative which has a hydroxyl group" and "compound which has two carboxyl groups" represented by Reaction Formulas 1-3 mentioned later It can also manufacture easily by esterification reaction with ". Here, the example of the said carboxyl group also contains the precursor which can become a carboxyl group, such as an acid halide group and an acid anhydride group.

Scheme 1

The reaction of Scheme 1 below is a partial esterification reaction between a compound represented by the formula (ii-1a) having two carboxyl groups and a compound represented by the formula (ii-1b) having a hydroxyl group. The partial esterification reaction means a reaction in which only a part of the carboxyl groups of the compound having a plurality of carboxyl groups in the molecule is esterified with a compound having a hydroxyl group.

Scheme 1

In Scheme 1,

X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by Chemical Formula t2,

R ₉₁ represents a hydrogen atom or a methyl group.

In the reaction of Scheme 1, the ratio between the compound represented by the formula (ii-1a) and the compound represented by the formula (ii-1b) is not particularly limited, but it is necessary to leave a carboxyl group in the compound of formula (ii-1) as the final target. Therefore, it is preferable to make the usage-amount of hydroxyl group less than the total amount of carboxyl group. Specifically, when the substance amount of the compound represented by the formula (ii-1a) is M1 and the substance amount of the compound represented by the formula (ii-1b) is M2, it is preferable that M1 / M2 = 1.

In the reaction of Scheme 1, when the amount of hydroxyl groups used is greater than the total amount of carboxyl groups, the esterification reaction is excessively promoted in the reaction mixture according to Scheme 1, which makes it difficult to partially leave carboxyl groups in the final target product. . In this case, it is necessary to stop the esterification reaction in the middle of the reaction so that one carboxyl group remains in the final object, but it is not easy to stop the reaction at the stage of the desired reaction rate, so it is preferable to appropriately adjust the amount of each organic group used. Do.

The said reaction rate can be grasped | ascertained by a well-known analysis means. Preferred examples of the analytical means for measuring the reaction rate include liquid chromatography, thin layer chromatography, and IR analyzer. In addition, in Reaction Formula 1, in order to manufacture the compound represented by general formula (ii-1) which is a final target object more accurately and refine | purify yields high, it is preferable to advance esterification reaction, measuring reaction rate suitably.

In the partial esterification reaction of Scheme 1, an esterification catalyst can also be used from the viewpoint of promoting the reaction. An esterification catalyst means the catalyst which activates the esterification reaction of carboxylic acid and alcohol. Preferable examples of such esterification catalyst include, but are not particularly limited to, photoacid, organic acid and Lewis acid, and known compounds can be used as the esterification catalyst. Examples of the mineral acid include hydrochloric acid and sulfuric acid. Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. In addition, examples of the Lewis acid include boron trifluoride and aluminum trichloride.

It is preferable that the usage-amount of the said esterification catalyst is sufficient quantity in order to accelerate | stimulate such partial esterification reaction. From the viewpoint of accelerating the partial esterification reaction, the amount of the esterification catalyst to be used is preferably 0.001 to 50% by mass and more preferably 0.01 to 30% by mass based on the total mass of the reaction mixture.

In the partial esterification reaction, water is generated during the reaction. At this time, in order to promote such a reaction, it is preferable to remove water as a by-product from the reaction mixture. The method of removing water in the reaction mixture is not particularly limited, but azeotropes water with the solvent using a solvent having a boiling point equivalent to water, such as benzene or toluene, or a molecular sieve, for example. and a method of using a dehydrating agent such as a molecular sieve.

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

Examples of the hydrocarbon solvent include n-hexane, benzene or toluene. Examples of the ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate or butyl acetate. Examples of the ether solvent include diethyl ether, tetrahydrofuran or dioxane. In addition, examples of the halogen solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or palen. These solvents may be used alone or in combination of two or more.

Although the reaction temperature of Reaction Formula 1 is not specifically limited, From a viewpoint of advancing the said partial esterification reaction efficiently and fully in a short time, it is preferable to make it substantially constant within the range of 50-150 degreeC, and to set it as 70-120 degreeC. It is more preferable.

The reaction time of Scheme 1 can be appropriately set according to the type, combination, and amount of use of the reaction temperature, the compound represented by the formula (II-1a), the compound represented by the formula (ii-1b), or the reaction solvent, and the like. It doesn't work. In consideration of the progress state of such partial esterification reaction, etc., it is preferable to carry out in the range of several minutes-100 hours, It is more preferable to set it as 0.5 to 50 hours, It is especially preferable to set it as 1 to 20 hours.

Scheme 2

As shown below, the reaction of Scheme 2 is a partial esterification reaction of a compound represented by the formula (ii-1c) having two acid halide groups with a compound represented by the formula (ii-1b) having a hydroxyl group, and a reaction mixture. It is a two-step reaction which hydrolyzes the acid halide group which remain | survives in the inside, and produces | generates the compound of general formula (II-1) which is a final target object.

Scheme 2

In Scheme 2,

X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by Chemical Formula t2,

X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

R ₉₁ represents a hydrogen atom or a methyl group,

COL represents an acid halide group, of which L represents halogen (Cl or Br).

In Scheme 2, it is necessary to leave a carboxyl group in the final target product. Therefore, in the partial esterification reaction which is the one-step reaction of Scheme 2, the amount of hydroxyl groups is preferably less than the total amount of acid halide groups. Here, when the amount of the hydroxyl group is larger than the total amount of the acid halide group, it is necessary to stop the reaction at the step of the desired reaction rate. However, since it is difficult to stop a reaction correctly at a desired reaction rate, it is not preferable.

The said reaction rate can be measured using a well-known analysis means. When reaction rate is suitably measured while advancing Reaction Formula 2, it becomes possible to stop or advance reaction in the step of desired reaction rate. Examples of such analysis means include liquid chromatography, thin layer chromatography or IR analysis apparatus.

The partial esterification reaction may be carried out in a solvent or in a solvent inert to such a reaction. Examples of such a solvent include a hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, and a halogen solvent.

Examples of the hydrocarbon solvent include n-hexane, benzene or toluene. Examples of the ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate or butyl acetate. Examples of the ether solvent include diethyl ether, tetrahydrofuran or dioxane. In addition, examples of the halogen solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or palen. These solvents may be used alone or in combination of two or more.

In the partial esterification reaction, hydrogen halide (for example, hydrogen chloride, etc.) is generated as a by-product by the reaction of an acid halogen group and a hydroxyl group. Since such hydrogen halide may deteriorate the properties of the reaction product, it is preferable to remove the hydrogen halide from the reaction mixture as much as possible. The method for removing the hydrogen halide is not particularly limited, and a known method may be used. However, the hydrogen dehalogenation agent is useful from the characteristics such as ease of handling.

Preferable examples of the dehalogenated hydrogen agent include an organic base compound or an inorganic base compound. Examples of the organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO) and 1,8-diazabicyclo [5.4.0] undeka-7-yen (DBU) is included. Examples of the inorganic base compound include sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium oxide. These compounds can also be used individually or in combination of multiple types.

The amount of the dehydrohalogenating agent used is not particularly limited and is preferably an amount sufficient to remove hydrogen halide generated in the reaction mixture. From this viewpoint, it is preferable that it is 0.1-10 mol with respect to 1 mol of hydroxyl groups, as for the usage-amount of the dehydrogenide agent, it is more preferable that it is 0.5-5 mol, and it is especially preferable that it is 1-3 mol.

In reaction formula 2, the hydrolysis reaction which is the reaction of the second stage is performed by adding water to the reaction mixture obtained at the end of the partial esterification reaction of the first stage. The method of adding water to the reaction mixture after the partial esterification reaction is complete is not specifically limited, Water may be added collectively or may be dripped. Especially, the latter method by dripping is preferable from a viewpoint of advancing reaction slowly.

From the viewpoint of accelerating the hydrolysis reaction, the amount of water used in the hydrolysis reaction is preferably 1 to 100 moles, more preferably 5 to 50 moles with respect to 1 mole of the acid halide group remaining in the reaction mixture.

The said hydrolysis reaction can advance or stop a reaction by confirming the reaction rate in a reaction mixture by a well-known analysis means at the time of dripping water, and continuing or stopping dripping of water at a desired reaction rate. Examples of the analyzing means include liquid chromatography, thin layer chromatography, and IR analysis apparatus.

Further, in the hydrolysis reaction, hydrogen halide (for example, hydrogen chloride, etc.) is produced as a by-product by reaction between the remaining acid halide and water to be added, but the hydrogen halide is a characteristic of the reaction product. There is a risk of deterioration. Therefore, it is preferable to remove the hydrogen halide generated in the reaction mixture as much as possible. Although the method of removing hydrogen halide is not specifically limited, From a viewpoint of workability and availability, a dehalogenation hydrogen agent is used preferably.

Examples of the dehalogenated hydrogenating agent include an organic base compound or an inorganic base compound. Specifically, examples of the organic base compound include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Diazabicyclo [5.4.0] undeka-7-ene (DBU) is included. On the other hand, examples of the inorganic base compound include sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide. These compounds can also be used individually or in combination of multiple types.

The usage-amount of the said dehydrohalogenation agent is not specifically limited, It is preferable to set it as the quantity which can fully remove the hydrogen halide which exists in a reaction mixture. From this point of view, the amount of the dehalogenated hydrogen agent is preferably 0.5 to 10 moles, more preferably 1 to 5 moles relative to 1 mole of the acid halide group remaining.

In Scheme 2, the reaction temperature at the time of the partial esterification reaction and the hydrolysis reaction is not particularly limited, but from the viewpoint of promoting partial esterification reaction, it is preferable to make it substantially constant within the range of -78 to 150 ° C. It is more preferable to set it as -20-100 degreeC, and it is especially preferable to set it as 0-80 degreeC.

The reaction time in the partial esterification reaction can be appropriately set according to the reaction temperature, the type of solvent used or combination thereof, the amount of the compound represented by the formula (ii-1b) and the compound represented by the formula (ii-1c), and the like. It is not limited. From a viewpoint of promoting such a reaction, it is usually preferable to set it as several minutes-100 hours, and it is more preferable that it is 30 minutes-50 hours. At this time, when the reaction time is set to 1 to 20 hours, such a reaction can be promoted without lowering the productivity, which is particularly preferable.

Scheme 3

As shown below, the reaction of Scheme 3 is a ring-opening esterification reaction between a compound represented by the formula (ii-1e) having an acid anhydride group and a compound represented by the formula (ii-1b) having a hydroxyl group. In the reaction of Scheme 3, the compound represented by the formula (II-1) in which the carboxyl group remains by the ring-opening esterification reaction is easily obtained. Therefore, in Reaction Formulas 1-3, it is most preferable as a manufacturing method of the compound represented by the said General formula (ii-1).

Scheme 3

In Scheme 3,

X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by Chemical Formula t2,

X ₄₂ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

R ₉₁ represents a hydrogen atom or a methyl group.

Although the compounding ratio of an acid anhydride group and a hydroxyl group in the said ring-opening esterification reaction is not specifically limited, From the viewpoint of promoting such ring-opening esterification reaction, the usage-amount of a hydroxyl group is 0.1-10 with respect to 1 mol of acid anhydride groups. It is preferable to set it as mole, It is more preferable to set it as 0.5-5 mol, It is especially preferable to set it as 0.8-3 mol.

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

Examples of the hydrocarbon solvent include n-hexane, benzene, toluene or xylene. Examples of the ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate or butyl acetate. Examples of the ether solvent include diethyl ether, tetrahydrofuran or dioxane. Examples of the halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or palene. In addition, examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

In the said ring-opening esterification reaction, you may use the catalyst which activates this reaction as needed. Examples of such a catalyst include organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organophosphorus salt compounds, imidazole compounds, and organometallic compounds.

Examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compounds include triethylamine and triethanolamine. Examples of the quaternary ammonium salt compound include trimethylammonium chloride and triethylbenzylammonium chloride. Examples of the organophosphorus compound include tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. 2-methylimidazole is contained in the example of the said imidazole compound. In addition, cobalt octenate is contained in the example of the said organometallic compound. These compounds can also be used individually or in combination of multiple types.

It is preferable to carry out the usage-amount of the said catalyst in the range of 0.01-10.0 mass% with respect to the mass of a reaction mixture from a viewpoint of obtaining sufficient reaction rate at the time of reaction, and it is more preferable to set it as 0.01-5.0 mass%.

The reaction temperature in the ring-opening esterification reaction is not particularly limited, and from the viewpoint of advancing such a reaction efficiently and effectively, it is preferable to make it substantially constant within the range of 0 ° C to 200 ° C, and to be 0 to 150 ° C. It is more preferable.

The reaction time in the ring-opening esterification reaction may be appropriately set according to the reaction temperature, the amount of use of the compound represented by the formula (ii-1b), the compound represented by the formula (ii-1e), or the type or combination of the solvents. Do not. It is preferable to set it as several minutes-several ten hours from a viewpoint of advancing such reaction efficiently and effectively.

In addition, in Reaction Formula 3, reaction can be advanced or stopped at arbitrary reaction rates, confirming reaction rate by a well-known analysis means. Examples of such analytical means include liquid chromatography, thin layer chromatography, and IR analysis apparatus.

[Compound represented by Formula ii-2]

Next, the compound represented by the said general formula (ii-2) is demonstrated. The compound represented by the formula (ii-2) is a (meth) acryloyl derivative having a compound represented by the formula (ii-1b) used in Schemes 1 to 3 having a hydroxyl group represented by the following formula (ii-2a) It is prepared by replacing with.

[Formula ii-2a]

In the 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 Chemical Formula t3, X ₆₂ represents an alkylene group having 1 to 10 carbon atoms,

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

Scheme 4

The compound represented by Chemical Formula ii-2a is prepared according to Scheme 4 below.

Scheme 4

In Scheme 4,

R ₉₂ and R ₉₃ each independently represent a hydrogen atom or a methyl group,

X ₆₁ represents a group represented by Chemical Formula t3, X ₆₂ represents an alkylene group having 1 to 10 carbon atoms,

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

The reaction of Scheme 4 has a hydroxyl group by ring-opening esterification reaction of the compound represented by the formula (ii-2b) having a glycidyl ether group and the compound represented by the formula (ii-2c) having an alcohol group. It is a reaction for synthesizing the (meth) acryloyl derivative represented by the formula (ii-2a).

The ring-opening esterification reaction of Scheme 4 can also be carried out in a solvent or in a solvent inert to such a reaction. Examples of such a solvent include hydrocarbon solvents such as n-hexane, benzene, toluene or xylene; Ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; Ester solvents such as diethyl ether, tetrahydrofuran or dioxane; Halogen-based solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or palene; Polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

In the said ring-opening esterification reaction, you may use the catalyst which acts on activation of this reaction as needed. Examples of such a catalyst include organic phosphine compounds such as triphenylphosphine; Tertiary amines such as triethylamine triethanolamine; Quaternary ammonium salts such as trimethylammonium chloride and triethylbenzylammonium chloride; Organic phosphates such as tetrabutyl phosphonium bromide and tetraphenyl phosphonium bromide; Imidazoles such as 2-methylimidazole; Organometallic compounds, such as cobalt octenate, are included. These catalysts may be used alone or in combination of two or more.

From the viewpoint of obtaining a sufficient reaction rate during the reaction, the amount of the catalyst used is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 5.0 mass%, based on the total mass of the reaction mixture in Scheme 4. . In the present invention, when a plurality of kinds of activating solvents are used, their total amount is regarded as the amount of the catalyst used.

The reaction temperature in the said ring-opening esterification reaction is not specifically limited, What is necessary is just enough temperature to advance such reaction. It is preferable to make it substantially constant in the range of 0-200 degreeC, and, as for the said reaction temperature, it is more preferable to set it as 0-150 degreeC.

The reaction time in the ring-opening esterification reaction is the amount of the compound represented by the formula (ii-2b) and the compound represented by the formula (ii-2c) used as the reaction temperature or the raw material, or the kind, the combination, the amount of the solvent, the catalyst, or the like. It can set suitably according to these etc. and it does not specifically limit. From a viewpoint of fully advancing such reaction, it is preferable to set it as several minutes-several ten hours normally.

In addition, in Reaction Formula 4, reaction can be advanced or stopped at arbitrary reaction rates, confirming reaction rate by a well-known analytical means. Examples of the analyzing means include liquid chromatography, thin layer chromatography, and IR analysis apparatus.

Scheme 5

Preferable 2nd (a) component of this invention can be obtained by reaction shown by following Reaction Formula 5, for example.

Scheme 5

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,

X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by Chemical Formula t2,

R ₇₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R ₉₁ represents a hydrogen atom or a methyl group.

The reaction of Scheme 5 is carried out by sequentially ring-opening esterification reaction using a compound represented by the above formula (VII-1) having three glycidyl groups and a compound represented by the above formula (ii-1) having a carboxyl group as raw materials. This is a reaction (also referred to as "sequential ring-opening esterification reaction") which has a glycidyl group and a (meth) acryloyl group in a molecule | numerator and produces | generates the compound represented by General formula (X-2).

In the sequential ring-opening esterification reaction, first, the glycidyl group and the carboxyl group in the compound represented by the formula (ii-1), which the compound represented by the formula (VII-1), are used as starting materials, The reaction results in the formation of a compound of formula VIII, which is a bifunctional epoxy resin. Further, the compound represented by the general formula (VII-1) and the compound represented by the general formula (ii-1) are subjected to ring-opening esterification to finally produce a compound represented by the general formula (X-2).

Since the solubility with respect to a liquid crystal is suppressed low, the compound represented by the said Formula (VII-2) is a preferable high molecular weight body. Moreover, since it has a glycidyl group in a molecule | numerator, and its reactivity with respect to an epoxy hardening | curing agent is high, it shows high sclerosis | hardenability also in the place like a light shielding area | region.

In the sequential ring-opening esterification reaction, the compounding ratio of glycidyl group and carboxyl group is not particularly limited, but in Scheme 5, the compound of formula (X-1) which is a product during the reaction and the compound of formula (X-2) as the final target It is necessary to leave glycidyl groups. Therefore, it is preferable to make the usage-amount of a carboxyl group less than the usage-amount of a glycidyl group. Specifically, the amount of the compound represented by Formula (ii-1) is preferably 1 to 2.8 moles, more preferably 1.3 to 2.5 moles, relative to 1 mole of the compound represented by Formula (X-1).

On the other hand, in Scheme 5, when the amount of the carboxyl group is used more than the amount of the glycidyl group, the reaction is promoted, so that all three carboxyl groups of the compound represented by the formula By reacting, there is a very high possibility of producing a compound represented by the following formula (VII). Since the compound represented by the formula (VIII) is a high molecular weight substance, its solubility in liquid crystals is suppressed low and does not have a glycidyl group having high reactivity with an epoxy curing agent. Therefore, since such a compound is concerned about low sclerosis | hardenability, it is not suitable as a raw material of a liquid crystal sealing agent.

In order to leave the glycidyl group partially in the compound represented by the formula (VII-1) and the compound represented by the formula (X-2), it is necessary to stop the reaction at the step of the desired reaction rate, but to stop the reaction at the precisely desired reaction rate is It is difficult. Therefore, when carrying out Reaction Scheme 5, it is preferable to adjust the compounding ratio of glycidyl group and carboxyl group as mentioned above.

[Formula ⅳ]

X ₄₂ in Formula (X) is

An alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 6 carbon atoms,

X ₄₁ represents an alkylene group having 1 to 10 carbon atoms or a group represented by Chemical Formula t2,

R ₉₁ represents a hydrogen atom or a methyl group.

The said reaction rate can be confirmed by a well-known analysis means. Examples of the analyzing means include liquid chromatography, thin layer chromatography, and IR analyzer.

The sequential ring-opening esterification reaction can be carried out in a solvent-free or in a 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 hydrocarbon solvent include n-hexane, benzene, toluene or xylene. Examples of the ketone solvent include acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate or butyl acetate. Examples of the ether solvent include diethyl ether, tetrahydrofuran or dioxane. Examples of the halogen-based solvent include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or palene. In addition, examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

In the sequential ring-opening esterification reaction, a catalyst which acts on activation of such a reaction may be used, if necessary. Examples of such a catalyst include organic phosphine compounds, tertiary amine compounds, quaternary ammonium salt compounds, organophosphorus salt compounds, imidazole compounds, and organometallic compounds.

Of the catalysts, examples of the organic phosphine compound include triphenylphosphine. Examples of the tertiary amine compounds include triethylamine and triethanolamine. Examples of the quaternary ammonium salt compound include trimethylammonium chloride and triethylbenzylammonium chloride. Examples of the organophosphorus compound include tetrabutylphosphonium bromide and tetraphenylphosphonium bromide. 2-methylimidazole is contained in the example of the said imidazole compound. Examples of the organometallic compound include cobalt octenate. These compounds can also be used individually or in combination of multiple types.

From the viewpoint of obtaining a sufficient reaction rate during the reaction, the amount of the catalyst used is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 5.0 mass%, based on the total mass of the reaction mixture in Scheme 5. .

Although the reaction temperature in the said sequential ring-opening esterification reaction is not specifically limited, What is necessary is just enough temperature to advance such reaction, It is preferable to make the said reaction temperature substantially constant within the range of 0-200 degreeC, and 0-150. It is more preferable to set it as ° C.

The reaction time in the sequential ring-opening esterification reaction can be appropriately set depending on the reaction temperature, the amount of the compound to be used, the kind, the combination, the amount of use of the solvent, the catalyst, and the like, and is not particularly limited. From the viewpoint of promoting such a reaction, it is preferable to set it as several minutes to several ten hours.

As shown by Scheme 5, the form which manufactures the compound which has glycidyl group and a (meth) acryloyl group in a molecule | numerator by sequential ring-opening esterification reaction is not limited to the above. That is, as the starting component (i), in addition to the formula (X-1), the formula (X-2), (X-3) or (X-4) may be used, and as the (ii) component represented by the formula (ii-1), In addition to the compound represented by the formula (ii-1), acrylic acid and methacrylic acid can be used. These compounds can be suitably selected and used in combination.

It is preferable that the (a) component of this invention exists in the range of 10-13 (cal / cm <3>) ^1/2 of the theoretical solubility parameter (SP value) of Fedors. There are various methods and calculation methods for calculating the solubility parameter (SP value), but the theoretical solubility parameter used in the present invention is preferably based on the calculation method devised by Fedors (Journal of the Japanese Adhesion Society, vol. 22, no. 10 (1986) (53) (566) (see Journal of Adhesion Society of Japan, et al.). Since the value of density is unnecessary in the said calculation method, a solubility parameter can be calculated easily. The theoretical solubility parameter (SP value) of the said Fedors is computed with the following formula | equation.

Here, when solubility parameter (SP value) exists in the said range, since the solubility of the compound represented by the said Formula (VII) of (a) component to liquid crystal becomes small, and the possibility that a liquid crystal may be contaminated is suppressed low, a liquid crystal display panel The display property of is high and becomes favorable.

When (a) component of this invention is synthesize | combined using a some compound as a raw material, theoretical solubility parameter (SP value) can be computed based on the sum of the mole fractions of each raw material mixed. It is preferable that the theoretical solubility parameter computed here is in the above-mentioned range.

Below, the component which can be used together with (a) component mentioned above as a raw material of a liquid crystal sealing agent is demonstrated.

(b) heat latent curing agent

The heat latent curing agent of the present invention does not react with functional groups such as epoxy groups in a state of preserving such resins (room temperature, visible light, etc.) even when mixed with a main material such as an epoxy resin. The hardening | curing agent which shows reaction activity with respect to a functional group by means of.

By including such a heat latent hardener in a liquid crystal sealing agent, the viscosity stability of a liquid crystal sealing agent improves. Thereby, since the viscosity stability at room temperature of such a liquid crystal sealing agent is maintained favorable, it can be used stably over a long time when filling a liquid crystal sealing agent in a screen printing machine or a dispenser, and drawing a sealing pattern on a board | substrate. Thus, when the usable time of a liquid crystal sealing agent becomes long, the improvement of productivity by manufacture of a liquid crystal display panel can be implement | achieved.

As the heat latent curing agent of the present invention, a heat latent epoxy curing agent that acts as a curing accelerator for the epoxy group in the component (a) and the epoxy resin (e) described later is preferably used. A heat latent epoxy resin means the compound which has an epoxy group as a functional group, and has heat potential.

As the heat latent curing agent of the present invention, a known one can be used. Especially, the amine type thermal latent hardener which has an amino group in a molecule | numerator is preferable. An amine type heat latent hardener means the compound which has an amino group in a molecule | numerator, and shows heat potential. Such amine-based thermal latent curing agents do not react with epoxy groups near room temperature, but react rapidly with epoxy groups as heat is applied. Moreover, since the hardened | cured material obtained by the reaction of an amine type thermal latent hardener and an epoxy resin generally is a crosslinked polymer, it has low solubility to a liquid crystal. The hardening rate with an amine changes with the kind of amine, compounding quantity, the kind of epoxy resin, etc. However, the amine heat latent curing agent preferably used in the present invention is not particularly limited, and may be appropriately selected from known compounds as the amine heat latent curing agent.

Preferred examples of the amine heat latent curing agent include organic acid dihydrazide compounds, imidazoles and derivatives thereof, dicyandiamides, aromatic amines, epoxy modified polyamines, polyaminoureas, and the like. These can also be used individually or in combination of multiple types.

Moreover, as a heat | fever latent hardening | curing agent, it is especially preferable that the softening point temperature by the melting point or the round ball method is 75 degreeC or more. Since the liquid crystal sealing agent containing such a thermal latent curing agent is more preferably maintained in viscosity stability at room temperature, the usable time in manufacturing a liquid crystal display panel becomes longer.

Examples of the amine heat latent curing agent having a softening point temperature of 75 ° C. or higher according to the melting point or the ring-opening method include dicyandiamide compounds, organic acid dihydrazide and imidazole derivatives.

Examples of the dicyandiamide compounds include dicyandiamide (melting point 209 ° C). Examples of the organic acid dihydrazide include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.) . Examples of the imidazole derivatives include 2,4-diamino-6- [2'-ethylimidazolyl- (1 ')]-ethyltriazine (melting point 215-225 ° C), 2-phenylimidazole ( Melting point 137-147 degreeC) is included. These compounds can also be used individually or in combination of multiple types.

It is preferable that it is 1-25 mass parts with respect to 100 mass parts of liquid crystal sealing agents, and, as for the compounding quantity of a thermal latent hardening | curing agent, it is more preferable that such compounding quantity is 5-15 mass parts. When the compounding quantity of a heat | fever latent hardening | curing agent exists in the said range, the viscosity stability of a liquid crystal sealing agent is favorable. Moreover, when such a liquid crystal sealing agent is applied to a liquid crystal display panel, since the adhesive strength of the hardened liquid crystal sealing agent and a board | substrate is high, the adhesive reliability of a liquid crystal display panel improves. It is preferable that the heat | fever latent hardening | curing agent used for this invention is given the high purity treatment by the water washing method, the recrystallization method, etc.

The liquid crystal sealing agent of this invention containing such a thermal latent hardening | curing agent is useful as a one-liquid type. The one-liquid type liquid crystal sealing agent is uniformly mixed in advance before the use of a main component such as an epoxy resin and a curing accelerator component such as a heat latent curing agent, and refers to a liquid crystal sealing agent excellent in storage stability. Excellent storage stability means that hardening reaction hardly progresses even if a liquid-crystal sealing agent is preserve | saved at room temperature or less. It is preferable that the viscosity increase rate at the time of storing a liquid crystal sealing agent at 25 degreeC specifically, for 5 days is 2 times or less of the viscosity of the liquid crystal sealing agent before storage.

(c) radical polymerization initiator

The radical polymerization initiator of the present invention refers to a compound that absorbs energy by light or heat to generate radicals. Examples of the radical polymerization initiator include an optical radical polymerization initiator and a thermal radical polymerization initiator.

In this invention, it is preferable to use an optical radical polymerization initiator as said (c) component. The photoradical polymerization initiator refers to a compound that generates radicals by being irradiated with light, that is, a compound that absorbs and decomposes light energy to generate radical species. Since the liquid crystal sealing agent containing such an optical radical polymerization initiator becomes hard by light irradiation, when used for the liquid crystal dropping system, hardening processes, such as an aftercure, are unnecessary, and also the hardening time of a liquid crystal sealing agent can be shortened. As a result, an improvement in productivity can be realized.

The radical photopolymerization initiator is not particularly limited and known compounds can be used. Examples thereof include benzoin compounds, acetophenone compounds, benzophenone compounds, thiocein tones compounds, α-acyl oxime ester compounds, benzoin compounds, benzoin ether compounds, phenylglyoxylate compounds, Benzyl compounds, azo compounds, anthraquinones compounds, diphenylsulfide compounds, acylphosphine oxide compounds, organic pigment compounds, and iron-phthalocyanine compounds. These can also be used individually or in combination of multiple types.

In this invention, a thermal radical polymerization initiator can also be used as said (c) component as mentioned above. The thermal radical polymerization initiator refers to a compound that is heated to generate radicals, that is, a compound that absorbs and decomposes thermal energy to generate radical species.

When such a thermal radical polymerization initiator is used in combination with an optical radical polymerizer to prepare a liquid crystal sealing agent, the liquid crystal sealing agent can be sufficiently cured in a short time by bonding the substrate and then temporarily curing with light and then further heating. At this time, when the liquid crystal sealing agent is cured only with light, in the light shielding region where light is not directly irradiated, the liquid crystal sealing agent may remain as an uncured portion, but if heat is used at the time of curing, the liquid crystal sealing may be used regardless of the light shielding region. It can harden to every corner of a product. Therefore, when such a liquid crystal sealing agent is applied to the liquid crystal display panel, a liquid crystal display panel having very low liquid crystal contamination property and excellent adhesive strength between the cured liquid crystal sealing agent and the substrate can be obtained.

A thermal radical polymerization initiator is not specifically limited, A well-known compound can be used. Examples thereof include organic peroxides, azo compounds, substituted ethane compounds, benzoin compounds, benzoin ether compounds, and acetphenone compounds.

Examples of the organic peroxide include compounds classified into ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxy dicarbonate.

Examples of organic peroxides are shown below. The numbers in parentheses are the 10 hour half-life temperatures (see Wakoponyaku Catalog, API Corporation Catalog and Polymer Handbook described above). In addition, examples of ketone peroxides include methyl ethyl ketone peroxide (109 ° C) and cyclohexanoperoxide (100 ° C).

Examples of the azo compound include water-soluble azo-based thermal radical polymerization initiators, oil-soluble azo-based thermal radical polymerization initiators, and polymeric azo-based thermal radical polymerization initiators.

Examples of the water-soluble azo-based thermal radical polymerization initiator include 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate (46 ° C) and 2,2'-azo Bis [N- (2-carboethyl) -2-methylpropionamidine] hydrate (57 ° C), 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline -2-yl] propane} dihydrochloride (60 ° C.), 2,2′-azobis (1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride (67 ° C.), 2 , 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (87 ° C), 2,2'-azobis [2- (2-imidazolin-2-yl) pro Payne] dihydrochloride (44 ° C), 2,2'-azobis (2-methylpropionamidine) dihydrochloride (56 ° C), 2,2'-azobis [2- (2-imidazoline- 2-yl) propane] (61 ° C.), 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} (80 ° C.) ) Is included.

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

Examples of the polymer azo-based thermal radical polymerization initiator include a polydimethylsiloxane unit-containing polymer azo-based thermal radical polymerization initiator and a polyethylene glycol unit-containing polymer azo-based thermal radical polymerization initiator. In addition, these thermal radical polymerization initiators can also be used individually or in combination of multiple types.

Regardless of whether the type of energy for generating radicals is light or heat, the blending amount of the component (c) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal sealing agent. When the compounding quantity of a radical polymerization initiator is 0.01 mass part or more, such a liquid crystal sealing agent can be hardened in a short time by irradiating a liquid crystal sealing agent with light and heat suitably selected. Moreover, when the compounding quantity of (c) component is 5 mass parts or less, the applicability | paintability of a liquid-crystal sealing agent is favorable, and the hardened | cured material hardened | cured uniformly by light irradiation is obtained.

(d) filler

The filler of this invention means the filler used for the purpose of improving the adhesive reliability of a liquid crystal sealing agent by improving the viscosity control of the liquid crystal sealing agent, the strength improvement of the hardened | cured material which hardened the liquid crystal sealing agent, or a linear expansion property.

The filler that can be preferably used in the present invention is not particularly limited, and known fillers that can be commonly used in the field of electronic materials are included. Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, asbestos powder Inorganic fillers such as quartz powder, mica, glass fibers, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride.

As a filler of this invention, the copolymer obtained by copolymerizing methyl polymethacrylate, polystyrene, the monomer which comprises these, and another monomer as long as it is a range which does not impair the characteristic of a liquid-crystal sealing agent, polyester microparticles | fine-particles, polyurethane microparticles | fine-particles, rubber Known organic fillers such as fine particles can also be used.

Especially, an inorganic filler is preferable from a viewpoint of improving linear expansion coefficient and shape retention. Among these inorganic fillers, silicon dioxide and talc are more preferable for reasons such as high UV transmittance. In addition, the filler used for the liquid crystal sealing agent of this invention may be what was graft-modified by epoxy resin, a silane coupling agent, etc. irrespective of an inorganic or organic.

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 shape. Moreover, the maximum particle diameter of a filler becomes like this. Preferably it is 6 micrometers or less, More preferably, it is 2 micrometers or less. The particle diameter of a filler can be measured by a laser diffraction method. When a liquid crystal sealing agent including a filler having such a particle size is used in the method for manufacturing a liquid crystal display panel, a liquid crystal cell having very good dimensional stability of a cell gap can be formed.

It is preferable to set it as 1-40 mass parts with respect to 100 mass parts of liquid crystal sealing agents except a filler, and, as for the compounding quantity of a filler, it is more preferable to set it as 10-30 mass parts. The liquid crystal sealing agent in which the compounding quantity of the filler was adjusted in this way has favorable applicability | paintability to a board | substrate. Moreover, a filler can also be used together with photocurable resin. Thus, the liquid crystal sealing agent which the filler and the photocurable resin used together harden | cures in a short time since photocurability is favorable. In addition, since the width of the cell gap is kept substantially constant, dimensional stability is improved.

The liquid crystal sealing agent of this invention may further contain either (e) epoxy resin and (f) acrylic compound, or (e) epoxy resin or (f) acrylic compound.

(e) epoxy resin

The epoxy resin of this invention means the compound which has one or more epoxy groups in a molecule | numerator. Examples of preferred epoxy resins used in the liquid crystal sealing agent of the present invention include aromatic polyvalent glycidyl ether compounds, novolac resins, novolac type polyvalent glycidyl ether compounds, and glycidyl ether compounds. .

Examples of the aromatic polyvalent glycidyl ether compound include aromatic diol compounds and compounds obtained by reaction of diol compounds obtained by modifying them with various glycols and epichlorohydrin. Examples of the aromatic diol compounds include bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins. In addition, examples of the glycol include ethylene glycol, propylene glycol and alkylene glycol.

Examples of the novolak resin include compounds derived from phenol or cresol and formaldehyde. Examples of the novolak-type polyvalent glycidyl ether compound include compounds obtained by the reaction of epichlorohydrin with polyphenol compounds represented by polyalkenylphenol, copolymers thereof and the like. Moreover, xylylene phenol resin is contained in the example of the said glycidyl ether compound.

Among them, examples of preferred (e) epoxy resins include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenol methane type epoxy resins, and triphenol ether type types. Epoxy resins, trisphenol type epoxy resins, dicyclopentadiene type epoxy resins, and biphenyl type epoxy resins are included. Examples of particularly preferable epoxy resins include these acrylic rubber-modified epoxy resins. These epoxy resins can be used individually or in combination of many types for the liquid crystal sealing agent of this invention.

Moreover, as for the epoxy resin used for this invention, it is preferable that the softening point temperature measured by the ring-ball method is 40 degreeC or more, and it is more preferable that the weight average molecular weight is 1000-10000. Such an epoxy resin has low solubility and diffusivity with respect to liquid crystal. Therefore, the liquid crystal display panel manufactured by the liquid crystal sealing agent in which such an epoxy resin was used has favorable display property.

The weight average molecular weight of an epoxy resin can be measured based on polystyrene as a standard by gel permeation chromatography (GPC), for example. Moreover, as an epoxy resin, what is highly purified by the molecular distillation method etc. and the impurity was removed is used preferably.

It is preferable to set it as 5-50 mass parts with respect to 100 mass parts of liquid crystal sealing agents, and, as for the compounding quantity of an epoxy resin, it is more preferable to set it as 10-30 mass parts. Such liquid crystal sealing agent has good heat resistance. However, when such a compounding quantity is less than 5 mass parts, hardening rate will become slow, and when 50 mass parts is exceeded, the heat resistance of a liquid-crystal sealing agent may fall.

(f) acrylic compounds

The acryl compound of this invention means the compound which has one or more acryl groups in a molecule | numerator. The acrylic compound of this invention also contains (meth) acrylic resin like methacryl resin. Examples of the acrylic compound include, but are not particularly limited to, acrylic acid ester and / or methacrylic acid ester monomers or oligomers thereof, and include known compounds. Thus, since the liquid-crystal sealing agent containing an acrylic compound becomes very water-resistant, when it is applied to a liquid crystal display panel, the adhesive strength of the hardened | cured material of such a liquid-crystal sealing agent and the board | substrate which comprises a liquid crystal display panel is very high, and moisture resistance A high quality liquid crystal display panel with excellent reliability can be obtained.

The following are contained in the preferable example of an acryl compound (f) component.

Diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol and polypropylene glycol; Diacrylates and / or dimethacrylates of tris (2-hydroxyethyl) isocyanurate; Diacrylates and / or dimethacrylates of diols obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; Diacrylate and / or dimethacrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A; Di or triacrylate and / or di or trimethacrylate of triols obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; Diacrylates and / or dimethacrylates of diols obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A; Tris (2-hydroxyethyl) isocyanurate triacrylate and / or trimethacrylate; Trimethylolpropane triacrylate and / or trimethacrylate, or oligomers thereof; Pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof; Polyacrylates and / or polymethacrylates of dipentaerythritol; Tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (methacryloxyethyl) isocyanurate; Polyacrylates and / or polymethacrylates of alkyl modified dipentaerythritol; Polyacrylates and / or polymethacrylates of caprolactone modified dipentaerythritol; Hydroxypivalate neopentylglycol diacrylate and / or dimethacrylate; Caprolactone modified hydroxypivalate neopentylglycol diacrylate and / or dimethacrylate; Ethylene oxide modified phosphoric acid acrylate and / or dimethacrylate; Ethylene oxide modified alkylated phosphoric acid acrylate and / or dimethacrylate; Neopentylglycols, trimethylolpropane, oligoacrylates and / or oligomethacrylates of pentaerythritol.

Moreover, in the example of an acryl compound (f) component, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a triphenol methane type epoxy resin, a triphenol ether type The resin which completely (meth) acrylated the epoxy resin obtained by making all epoxy groups, such as an epoxy resin, a trisphenol-type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin, react with (meth) acrylate acid Included. These compounds can also be used individually or in combination of multiple types.

When including an acrylic compound (f) component in a liquid crystal sealing agent, it is preferable to use together with an epoxy resin (e) component. At this time, it is preferable that the compounding quantity of (e) component is 20-200 mass parts with respect to 100 mass parts of (f) components. When such liquid crystal sealing agent is cured by light or heat, a cured product having a high glass transition temperature (Tg) is obtained. Tg of the hardened | cured material of a liquid crystal sealing agent can be measured with a dynamic viscoelasticity measuring apparatus (DMA). In addition, for the purpose of obtaining a high-purity liquid crystal sealing agent, it is preferable to use the thing (f) which was made highly purified by the water washing method, etc.

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

The (meth) acryl modified epoxy resin which has an epoxy group and a (meth) acryl group in frame | skeleton shows high compatibility with respect to the said (e) component. Therefore, the liquid crystal sealing agent containing a (meth) acryl modified epoxy resin and the said (e) component is excellent in high glass transition temperature (Tg), durability, and heat resistance. Moreover, the adhesive strength of the hardened | cured material of this liquid crystal sealing agent and the board | substrate which comprises a liquid crystal display panel becomes high.

As an example of the epoxy resin used as a raw material of a (meth) acryl modified epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a triphenol methane type epoxy resin, Triphenol ethane type epoxy resin, a trisphenol type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin are contained. Moreover, it is preferable that the (meth) acryl modified epoxy resin is highly purified by molecular distillation method, a washing method, etc.

(g) other additives

Moreover, an additive can also be included in the liquid crystal sealing agent of this invention as needed. Examples of the additive preferably used in the present invention include coupling agents such as thermal radical polymerization initiators and silane coupling agents, ion traps, ion exchangers, leveling agents, pigments, dyes, plasticizers, and antifoaming agents. These additives may be used alone or in combination of two or more depending on the application.

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

When preparing a thermosetting sealing agent, you may contain an organic solvent in order to improve dispenser coating property and screen printability. It is preferable that such an organic solvent has high compatibility with the epoxy resin which is (e) component, a boiling point exists in the range of 140-220 degreeC, and is inert with respect to an epoxy group. Examples of such organic solvents include ketone solvents, ether solvents and acetate solvents. These can also be used individually or in combination of multiple types.

[Preparation method of liquid crystal sealing agent]

The method of preparing the liquid crystal sealing agent of this invention is not specifically limited, A well-known technique can be used. In addition, examples of the means for mixing the components of the liquid crystal sealing agent include a double stirrer, a roll kneader, a twin screw extruder, a ball mill kneader, and a planetary stirrer, but a known kneading machine can be used without particular limitation. The liquid crystal sealing agent suitably mixed by either method is filtered through a filter to remove impurities. Then, after the vacuum degassing treatment is performed, the glass bottle or the poly container is sealed and filled, and stored and transported as necessary.

[Manufacturing Method of Liquid Crystal Display Panel]

Next, the manufacturing method of the liquid crystal display panel of this invention is demonstrated. The liquid crystal sealing agent of this invention mentioned above is applicable also in any of a liquid crystal injection system and a liquid crystal dropping system. Below, the manufacturing method of the liquid crystal display panel of this invention which concerns on a liquid crystal injection system and a liquid crystal dropping system is demonstrated sequentially.

The manufacturing method of the liquid crystal display panel of this invention is a manufacturing method of the liquid crystal display panel manufactured by bonding two board | substrates which oppose through a liquid crystal sealing agent, (1) the pixel arrangement area | region by the liquid crystal sealing agent of this invention. A step of preparing one or more substrates having an edge-shaped display area formed so as to be enclosed, (2) dropping a liquid crystal onto the other substrate or in the display area in an uncured state, and (3) dropping the liquid crystal And a step of overlapping the substrate with the other substrate, and (4) applying either light and heat, or light or heat to the liquid crystal sealing agent sandwiched between the two substrates.

In the process of (1), the liquid crystal sealing agent is apply | coated to either one of two board | substrates, and the board | substrate which arrange | positioned the edge-shaped display area is prepared. Here, the edge formed by the liquid crystal sealing agent is formed to surround the pixel array region.

As the liquid crystal sealing agent, the liquid crystal sealing agent according to the present invention as described above is useful. The liquid crystal sealing agent not only forms an edge such as a display area, but also acts as an adhesive for bonding two substrates at regular intervals. Moreover, although the example of the method of apply | coating a liquid crystal sealing agent on a board | substrate includes application | coating by a dispenser and application | coating by screen printing, it does not specifically limit but a well-known technique can be used. When manufacturing a small liquid crystal display panel, application | coating by screen printing is preferable from a viewpoint of productivity improvement.

Examples of the two substrates used for the liquid crystal display panel include a glass substrate on which TFTs are formed in a matrix, a substrate on which a color filter and a black matrix are formed. Examples of the substrate material include plastics such as glass, polycarbonate, polyethylene terephthalate, polyether sulfone, and PMMA.

An alignment film may be formed on the opposing surface of each substrate. It does not specifically limit as an oriented film, For example, what consists of a well-known organic aligning agent and an inorganic aligning agent can be used. In addition, the spacer may be sprayed on the substrate in advance. The spacer is generally used for spherical silica particles, and is effective in keeping the cell gap uniform. Usually, the in-plane spacer of the state sprayed on the board | substrate previously, or the spacer contained in the liquid crystal sealing agent is used. Moreover, the kind and size of a spacer are not specifically limited, A well-known thing may be used according to the magnitude | size of a cell gap desired.

In the process of (2), a suitable amount of liquid crystal is dripped on the inside of the edge used as an uncured display area, or the other board | substrate. Here, the other board | substrate with which a liquid crystal is dripped means a board | substrate different from the board | substrate containing a display area. In the case of dropping liquid crystal on the other substrate, the liquid crystal may be dropped into an area that can be a display area when the substrates are wrapped.

In addition, it is preferable that the dropping liquid crystal adjusts the drop amount of a liquid crystal according to the magnitude | size of an edge so that the dropped liquid crystal may enter in an edge. In this way, when a liquid crystal is dripped in an edge, the capacity of a liquid crystal does not exceed the capacity of the cell which is the space enclosed by the edge and the board | substrate after bonding. Therefore, excessive pressure is not applied to the edge and the seal forming the edge is not damaged.

In the process of (3), the board | substrate with which liquid crystal was dripped overlaps with the other board | substrate. Here, it is preferable that superimposition is performed under reduced pressure by a vacuum bonding apparatus etc. By returning the two stacked substrates to atmospheric pressure in the next step, the substrates can be bonded to each other using an air pressure difference.

In the process of (4), either light and heat, or light or heat are added to the liquid crystal sealing agent sandwiched between two board | substrates. Thereby, in a inside of a liquid crystal sealing agent, radical generate | occur | produces by the action of a radical polymerization initiator, and hardening reaction of a liquid crystal sealing agent advances because hardening reaction of a main body and a hardening agent is accelerated | stimulated.

In the process of said (4), the kind of light added to a liquid crystal sealing agent, irradiation time, the temperature or time at the time of heating, etc. are not specifically limited, What is necessary is just to select suitably according to the composition of a liquid crystal sealing agent, etc. For example, when hardening a liquid crystal sealing agent by heat, it is preferable to make heating temperature 40-90 degreeC and heating time 1-120 minutes from a viewpoint of promoting hardening of a liquid crystal sealing agent. Moreover, after heat-curing a liquid crystal sealing agent once as needed, after-cure for 30 to 90 minutes can also be performed at 110-150 degreeC. Although well-known heating apparatuses, such as an oven, a hotplate, and a hot press, are included in the example of the heating means of a liquid crystal sealing agent, It does not specifically limit.

The present invention may include a step of returning the two stacked substrates to atmospheric pressure after the step (3). Thus, when the board | substrate nested under pressure_reduction | reduced_pressure | reduced_pressure | pressure_reduction | reduced_pressure_pressure_reduction | reduced_pressure_pressure_reduced_pressure_pressure_reduced_pressure_pressure_reduced_pressure_pressure_reduced_pressure_pressure_pressure_reduced_pressure_pressure_pressure | pressure difference generate | occur | produces inside and outside of the edge, two board | substrates are pressed from both outer sides, and the board | substrate is joined.

Moreover, in the recent liquid crystal dropping system, in order to improve productivity, each liquid crystal is formed by forming several edges with a liquid crystal sealing agent on a board | substrate, and cutting the outer periphery of an edge after bonding two board | substrates together. The method of cutting out a display panel is employ | adopted. The present invention is also suitable for such a method.

The liquid-crystal sealing agent of this invention maintains high viscosity stability, the solubility with respect to liquid crystal is low, and the hardening | curing agent (a) component which has high sclerosis | hardenability, a thermal latent property, the radical polymerization initiator, and the filler are contained. When a liquid crystal display panel is manufactured by the liquid crystal dropping method using such a liquid-crystal sealing agent, even if there is a light-shielding area | region, hardening advances fully and it can advance work, maintaining storage stability and applicability high. Thereby, since there are very few uncured parts in the hardened | cured material of a liquid crystal sealing agent, as a result, the liquid crystal contamination is prevented and a liquid crystal display panel with high adhesive strength of the hardened | cured material of a liquid crystal sealing agent and a board | substrate can be obtained as a result. .

The degree to which the liquid crystal is contaminated in the liquid crystal display panel, that is, the liquid crystal contamination of the liquid crystal display panel can be evaluated based on the ΔNI point, which is a difference between the NI points. The NI point is a temperature when the liquid crystal phase changes from a nematic phase to an isotropic phase (isotropic phase). The phase transition temperature can be measured from the inflection point of the exothermic peak using a differential thermal analysis device. (DELTA) NI point is a difference between "the NI point of the uncontaminated liquid crystal" and the "NI point of the contaminated liquid crystal". When the raw material or liquid-crystal sealing agent with high liquid-crystal contamination is mixed with a liquid crystal, the absolute value of (DELTA) NI point will become large. On the other hand, when the liquid crystal contamination of a raw material or a liquid crystal sealing agent is low, the absolute value of (DELTA) NI point becomes low. Therefore, the smaller the ΔNI point, the lower the liquid crystal contamination.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples according to the present invention. However, this invention is not limited to the form shown below.

(a) A compound which contains a (meth) acryloyl group and glycidyl group in a molecule | numerator, and has a number average molecular weight 500-2000.

As the component (a), the compounds synthesized in the following Synthesis Examples 1 to 10 were used, respectively. Among these, the compound synthesized in Synthesis Examples 1 to 4 corresponds to the first component (a), and the compound synthesized in Synthesis Examples 7 to 10 corresponds to the second component (a). In addition, although the compound synthesize | combined in the synthesis examples 5 and 6 has predetermined organic group in a molecule, the number average molecular weight is out of the range of 500-2000.

In each synthesis example, the acid value of the reaction mixture taken at the arbitrary stage in the synthesis process was computed by the following method, and the synthesis reaction was advanced, confirming the progress of reaction suitably from the value of the calculated acid value. The said acid value dissolves the sample extract | collected suitably from the reaction mixture in the diethyl ether ethanol solution, and also adds the phenolphthalein ethanol solution; KOH's ethanol solution (0.1 N) was added dropwise until the obtained solution became colorless; Calculated from the amount of KOH consumed.

In addition, the number average molecular weight of the final target object obtained by each synthesis example was measured by the following method. The number average molecular weight was measured by 1) gel permeation chromatography (GPC) based on polystyrene and 2) electrolytic desorption mass spectrometry (FD-MS method).

Synthesis Example 1

In the synthesis example 1, the compound A1 containing a (meth) acryloyl group and glycidyl group was synthesize | combined by making glycerol acrylate methacrylate modified phthalic acid and bisphenol F diglycidyl ether react.

First, a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube was 74 g (0.5 mol) of phthalic anhydride, 271 g (0.5 mol) of glycerol acrylate methacrylate, and tributylammonium as a catalyst. 0.7 g of bromide and 0.5 g of phenothiazine were mixed as a polymerization inhibitor, heated to 80 ° C, and reacted for 1 hour, and further heated to 130 ° C and reacted for 2 hours.

To 276 g (0.4 mol) of this reaction product, 125 g (0.4 mol) of bisphenol F-type epoxy resin (manufactured by Epotto YDF-8170C Toto Kasei Co., Ltd.), 0.6 g of tributylammonium bromide as a catalyst, and hydroquinone as a polymerization inhibitor 0.1 g of monomethyl ether was placed in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, heated and mixed at 80 ° C, and blown with dry air. It was made to react until it became below. This reaction product was then column separated with silica gel to give compound A1. HPLC and NMR analysis of the obtained compound A1 confirmed that it was a compound containing a (meth) acryloyl group and glycidyl group.

In addition, when the number average molecular weight of Compound A1 was measured by GPC, the number average molecular weight of Compound A1 obtained as a single peak was 689. In addition, when the number average molecular weight of Compound A1 was measured by FD-MS method, it was single peak and was the same molecular weight (689).

Synthesis Example 2

In Synthesis Example 2, the (meth) acryloyl group and the article were reacted by reacting 2-hydroxyethyl acrylate-modified 4-methacryloyloxyethyltrimelitic acid with bisphenol F diglycidyl ether in the following manner. Compound A2 having a lycidyl group was synthesized.

First, in a 1000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 58 g of 2-hydroxyethyl acrylate (152 g (0.5 mol) of 4-methacryloyloxyethyl trimellitic anhydride) 0.5 mol), 0.7 g of tributylammonium bromide as a catalyst, 0.5 g of phenothiazine as a polymerization inhibitor were mixed, heated to 80 ° C for 1 hour, and further heated to 130 ° C for 2 hours. Subsequently, 168 g (0.4 mol) of this reaction product, 125 g (0.4 mol) of bisphenol F-type epoxy resin (manufactured by Epotto YDF-8170C DOTO Chemical Co., Ltd.), 0.6 g of tributylammonium bromide as a catalyst, and hydro as a polymerization inhibitor were used. 0.1 g of quinone monomethyl ether was added to a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube. After heating the obtained mixture to 80 degreeC, it was made to react until the acid value became 2 mgKOH / g or less, blowing dry air.

The reaction was diluted with 1000 g of ethyl acetate and concentrated after repeated washing with ultrapure water five times. This reaction product was then column separated with silica gel to give compound A2. HPLC and NMR analysis of the obtained compound A2 confirmed that it was a compound containing a (meth) acryloyl group and glycidyl group. Further, as a result of GPC analysis of compound A2, the number average molecular weight of compound A2 obtained as a single peak was 733. The number average molecular weight of compound A2 confirmed that it was a single peak and the same molecular weight also in the FD-MS method.

Synthesis Example 3

In the synthesis example 3, the compound A3 which has a methacryloyl group and glycidyl group was synthesize | combined by making 2-hydroxymethacrylate modified phthalic acid and bisphenol F diglycidyl ether react by the following method.

First, a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube was 74 g (0.5 mol) of phthalic anhydride, 65 g (0.5 mol) of 2-hydroxyethyl methacrylate, and tributylammonium as a catalyst. 0.7 g of bromide and 0.5 g of phenothiazine were mixed as a polymerization inhibitor, heated to 80 ° C, and reacted for 1 hour, and further heated to 130 ° C and reacted for 2 hours. After the reaction, the reaction solution was diluted with 1000 g of ethyl acetate, and washed with ultrapure water five times and concentrated. 111 g (0.4 mol) of this reaction product, 125 g (0.4 mol) of bisphenol F-type epoxy resin (manufactured by Epotto YDF-8170C DOTO Chemical Co., Ltd.), 0.6 g of tributylammonium bromide as a catalyst, hydroquinone mono as a polymerization inhibitor 0.1 g of methyl ether was added to a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube. After heating the obtained mixture to 80 degreeC, it was made to react until the acid value became 2 mgKOH / g or less, blowing dry air further.

The reaction was diluted with 1000 g of ethyl acetate and concentrated after repeated washing with ultrapure water five times. This reaction product was then column separated with silica gel to give compound A3. As a result of analyzing the composition of obtained compound A3 by HPLC and NMR, it was confirmed that it is a compound containing a methacryloyl group and glycidyl group. In addition, the result of GPC analysis of Compound A3 showed that the number average molecular weight of Compound A3 obtained as a single peak was 591. The number average molecular weight of compound A3 confirmed that it was a single peak and the same molecular weight also in the FD-MS method.

Synthesis Example 4

In the synthesis example 4, the compound A4 which has a (meth) acryloyl group and glycidyl group was synthesize | combined by making a carboxylic acid derivative and bisphenoxy ethanol fluorene diglycidyl ether react.

First, the 6-hexanolide adduct of 2-hydroxyethyl acrylate (Diesel Chemicals, brand name Plaque Cell FA3) was column purified using silica gel. 48 g of sodium hydride and 200 g of toluene were added to a 1000 ml five-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, a cooling tube, and a lot tube, and ice-cooled under a nitrogen stream. The solution which melt | dissolved 229 g (0.5 mol) of 6-hexanolide adducts of refine | purified 2-hydroxyethyl acrylate in 200 g of toluene was dripped over 2 hours.

After the dropwise addition of the solution was held for 1 hour while ice-cooling, the reaction mixture was filtered to remove unreacted sodium hydride. Then, 185 g (2 mol) of epichlorohydrin, 5 g of tetramethylammonium chloride, and 0.1 g of hydroquinone monomethyl ether were added to the reaction mixture, and the mixture was stirred for 3 hours at 70 ° C while blowing dry air.

Then, the reaction mixture after the reaction was rinsed five times with ultrapure water, and then heated and reduced in pressure at 120 ° C to remove excess epichlorohydrin and other impurities such as 6-hexane of 2-hydroxyethyl acrylate. The reaction product (A4a) of the olide adduct and epichlorohydrin was obtained. Subsequently, 206 g (0.4 mol) of this reaction product (A4a) and 6-((6-acryloyloxy) hexanoyloxy) hexanoic acid (products of Alonics M-5300 Doa Synthetic Co., Ltd.) (molecular weight) previously column-refined 300) 120 g (0.4 mol), 0.6 g of tributylammonium bromide as a catalyst, 0.1 g of hydroquinone monomethyl ether as a polymerization inhibitor, warmed to 80 ° C., and the acid value was 2 mgKOH while blowing dry air. It reacted until it became / g or less, and obtained reaction product (A4b).

Subsequently, 163 g (0.2 mol) of the obtained reaction product (A4b), 61 g (0.2 mol) of 4-methacryloyloxyethyl trimellitic anhydride, 0.5 g of phenothiazine as a polymerization inhibitor were mixed, and it heated at 80 degreeC, After making it react for 1 hour, it heated further at 130 degreeC and made it react for 2 hours, and obtained reaction product (A4c). Then, 112 g (0.1 mol) of this reaction product (A4c), 55 g (0.1 mol) of bisphenoxyethanol fluorene diglycidyl ether (manufactured by BPEF-G Osaka Gas Chemical Co., Ltd., molecular weight 550), as a catalyst 0.2 g of tributylammonium bromide and 0.1 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed in a 300 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a cooling tube, and heated to 80 ° C. . The reaction was carried out while blowing dry air until the acid value became 2 mgKOH / g or less. The obtained reaction product was column separated with silica gel to give compound A4.

HPLC and NMR analysis of the obtained compound A4 confirmed that it was a compound containing a (meth) acryloyl group and glycidyl group. Also, as a result of GPC analysis of compound A4, the number average molecular weight of compound A4 obtained as a single peak was 1670. In addition, the number average molecular weight of compound A4 confirmed that it was a single peak and the same molecular weight also in the FD-MS method.

Synthesis Example 5

In the synthesis example 5, the epoxy resin which methacryloyl-modified the bisphenol-A epoxy resin was synthesize | combined.

First, in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol A type epoxy resin (Epiclon 850CRP, Dainippon Ink and Chemicals, Inc.), 43 g of methacrylic acid, a catalyst 0.2 g of triethanolamine and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed together, and it heated and stirred at 110 degreeC for 5 hours, blowing dry air, and obtained the methacryl modified bisphenol-A epoxy resin. Compound A5 was obtained by repeating washing process of the obtained resin with ultrapure water 12 times. As a result of analyzing the obtained compound A5 by HPLC and NMR, it was confirmed that 50% of an epoxy group is methacryloyl-modified bisphenol-A epoxy resin. Moreover, the number average molecular weight was 427 as a result of GPC analysis of the obtained compound A5.

[Synthesis Example 6]

In the synthesis example 6, the epoxy resin in which the bisphenol F-type epoxy resin was acryloyl modified was synthesize | combined.

First, in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol F-type epoxy resin (Epiclon 850CRP, Dainippon Ink and Chemicals, Inc.), 37 g of acrylic acid, and a catalyst were used. 0.2 g of ethanolamine and 0.2 g of hydroquinone monomethyl ether were mixed as a polymerization inhibitor, and it heated and stirred at 110 degreeC for 12 hours, blowing in dry air, and obtained acrylic modified bisphenol-A epoxy resin. The obtained resin was repeated 12 times with the ultrapure water. As a result of analyzing the resin by HPLC and NMR, bisphenol A epoxy resin (Compound A6) in which 50% of the epoxy groups were acryloyl-modified was obtained. The number average molecular weight was 412 as a result of GPC analysis of the obtained compound A6.

[Synthesis Example 7]

In the synthesis example 7, the compound A7 which has a (meth) acryloyl group and glycidyl group was synthesize | combined by making a phenol novolak-type trifunctional epoxy resin and a (meth) acrylic acid derivative react.

First, in a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, a phenol novolak-type trifunctional epoxy resin (SR-HP3 Sakamoto Chemical Co., Ltd.) ), 142.4 g (0.3 mol) of methacrylic acid, 20.7 g (0.3 mol) of methacrylic acid, 73.3 g (0.3 mol) of compound B1 described later, 1.45 g of tributylammonium bromide as a catalyst, 0.01 g of phenothiazine was added as a polymerization inhibitor, and the mixture was heated and mixed at 80 ° C, and reacted for 15 hours until the acid value became 2 mgKOH / g or less while blowing dry air. Compound B1 used here is the reaction product of 2-hydroxyethyl methacrylate and succinic anhydride.

232 g of the obtained reaction solution was diluted with 900 g of toluene and 300 g of ethyl acetate. 222 g of Compound A7 was obtained by repeating the operation of washing the diluted reaction solution with 300 g / 1 of ultrapure water and concentrating until the electrical conductivity of the aqueous phase became 1 kPa / cm or less. FD-MS analysis of the obtained compound A7 showed a number average molecular weight of 804.

[Synthesis Example 8]

In the synthesis example 8, the epoxy resin which has a (meth) acryloyl group and glycidyl group was synthesize | combined by making a phenol novolak-type tetrafunctional epoxy resin and (meth) acrylic acid derivative react.

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, a phenol novolac tetrafunctional epoxy resin (YL-7284 Japan Epoxy Resin Co., Ltd. product) , 318 g (0.5 mol) of the number average molecular weight 636), 104 g (0.45 mol) of the compound B1 described later and 110 g (0.45 mol) of the compound B2, 2.1 g of tributylammonium bromide as a catalyst, 0.05 g of phenothiazine as a polymerization inhibitor Heated and mixed at 80 ° C. The reaction was carried out for 15 hours while blowing dry air until the acid value became 2 mgKOH / g or less. Compound B2 used here is the reaction product of 4-hydroxybutyl acrylate and succinic anhydride.

530 g of the obtained reaction solution was diluted using 1200 g of toluene and 600 g of ethyl acetate. 509 g of Compound A8 was obtained by repeating the operation of washing the diluted reaction solution with 500 g / 1 of ultrapure water ten times, and concentrating until the electrical conductivity of the aqueous phase became 1 kPa / cm or less. The number average molecular weight was 1111 when the obtained compound A8 was analyzed by FD-MS.

Synthesis Example 9

In the synthesis example 9, the epoxy resin which has a (meth) acryloyl group and glycidyl group was synthesize | combined by making a phenol novolak-type tetrafunctional epoxy resin and a (meth) acrylic acid derivative react with the following method.

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, a phenol novolac tetrafunctional epoxy resin (YL-7284 Japan Epoxy Resin Co., Ltd. product) , 318 g (0.5 mol) of number-average molecular weight 636) by FD-MS method, 425 g (0.9 mol) of compound B3 described later, 2.1 g of tributylammonium bromide as a catalyst, 0.05 g of phenothiazine as a polymerization inhibitor, and 80 The mixture was heated and mixed at a temperature of C, and reacted for 15 hours while the acid value was 2 mgKOH / g or less while blowing dry air. Compound B3 used here is a reaction product of caprolactone 3-mole modified methacrylate and succinic anhydride.

740 g of the obtained reaction solution was diluted using 1200 g of toluene and 600 g of ethyl acetate. 730 g of Compound A9 was obtained by repeating the operation of washing the diluted reaction solution with 600 g / 1 of ultrapure water ten times, and concentrating until the electrical conductivity of the aqueous phase became 1 kPa / cm or less. FD-MS analysis of the obtained compound A9 showed a number average molecular weight of 1770.

Synthesis Example 10

In the synthesis example 10, the epoxy resin which has a (meth) acryloyl group and glycidyl group was synthesize | combined by making a trifunctional epoxy resin and a (meth) acrylic acid derivative react.

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a cooling tube, VG-3102 (manufactured by Mitsui Chemicals, FD-MS) as a compound represented by the formula 184 g (0.40 mol) of the number-average molecular weight 460), 92 g (0.40 mol) of the compound B1 mentioned later, and 97.6 g (0.40 mol) of the compound B2 mentioned later, 2.0 g of tributylammonium bromide as a catalyst, phenothiazine 0.05 as a polymerization inhibitor g was added and heat-mixed at 80 degreeC. The reaction was carried out for 8 hours while blowing dry air until the acid value became 2 mgKOH / g or less.

370 g of the obtained reaction solution was diluted with 900 g of toluene and 300 g of ethyl acetate. And the operation which wash | cleaned this diluted reaction liquid with ultrapure water 300g / 1 time 10 times was repeated, and it concentrated until the electrical conductivity of an aqueous phase is 3 kPa / cm or less, and 361g of compound A10 was obtained. The number average molecular weight was 934 as a result of FD-MS analysis of the obtained compound A10.

Hereinafter, the synthesis example of the (meth) acrylic-acid derivative (B1-B3) used by the synthesis example mentioned above is demonstrated.

[Synthesis of Compound B1]

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a cooling tube, 420 g (4.2 mol) of succinic anhydride, 656 g (5.0 mol) of 2-hydroxyethyl methacrylate, phenothiazine as a polymerization inhibitor 0.05 g was mixed, and it heated at 110 degreeC and made it react for 5 hours. The reaction product was diluted with 2500 g of toluene, washed repeatedly with 800 g of ultrapure water six times, and concentrated to give 850 g of Compound B1. HPLC and NMR analysis of the obtained compound B1 confirmed that the compound B1 which is a reaction product of desired 2-hydroxyethyl methacrylate and succinic anhydride was obtained.

[Synthesis of Compound B2]

In a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 480 g (4.8 mol) of succinic anhydride, 577 g (4 mol) of 4-hydroxybutyl acrylate, and 0.05 g of phenothiazine as a polymerization inhibitor The mixture was mixed and warmed to 110 ° C to react for 5 hours. The reaction product was diluted with 2000 g of toluene, washed with water with 1000 g of ultrapure water five times, and concentrated to give 920 g of Compound B2. As a result of analyzing the obtained compound B2 by HPLC and NMR, it was confirmed that the compound B2 which is a reaction product of desired 4-hydroxybutyl acrylate and succinic anhydride is obtained.

[Synthesis of Compound B3]

To a 2000 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 120 g (1.2 mol) of succinic anhydride and a 3-mole adduct of 6-hexanolide of purified 2-hydroxyethyl methacrylate 472 g (1.0 mol) and 0.05 g of phenothiazine were mixed as a polymerization inhibitor, and it heated at 110 degreeC and made it react for 5 hours. 3-mole adduct of 6-hexanolide of refined 2-hydroxyethyl methacrylate is a 3-mole adduct of 6-hexanolide of 2-hydroxyethyl methacrylate which is a commercial item (plaque cell FM3 diecel chemical ( Note) is a column purified product).

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

(b) heat latent curing agent

As the heat latent curing agent, (i) 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (manufactured by Amicure VDH-J Ajinomoto Fine Techno Co., Ltd.), (ii) adipic acid Two types of dihydrazide (ADH Nippon Finechem Co., Ltd. product) were appropriately selected and used.

(c) radical polymerization initiator

As a radical polymerization initiator, 1-hydroxy-cyclohexyl phenyl- ketone (Irgacure 184 Chivas Specialty Chemicals Co., Ltd. product) which acts as an optical radical polymerization initiator was used.

(d) filler

As a filler, spherical silica (primary average particle diameter 0.7 micrometer) (admapaine A-802 Admatex Co., Ltd. product) was used.

(e) epoxy resin

As an epoxy resin, o-cresol novolak-type solid epoxy resin (EOCN-1020-75 Nihon Kayaku Co., Ltd. product) was used.

(f) acrylic compounds

As (f) component, (i) dimethacrylate (Epoxy ester 3000M Kyoeisha Chemical Co., Ltd.) which is bisphenol-A resin is diluted with toluene and ultrapure water, and it washes 12 times, and is highly purified. Compound, (ii) bisphenol A, EO adduct diacrylate (Biscote # 700 Osaka Organic Chemicals Co., Ltd.) was diluted with toluene and ultrapure water and washed 12 times to repeat the high purity of the compound. It used suitably and selected.

(g) other additives

As an additive, (gamma) -glycidoxycitraimethoxysilane (KBM 403 Shin-Etsu Chemical Co., Ltd. product) marketed as a silane coupling agent was used.

In addition, in each Example and the comparative example, the viscosity stability of the liquid crystal sealing agent, the adhesive strength of the liquid crystal sealing agent, and the displayability of the liquid crystal display panel were measured and evaluated, respectively, and the characteristic of the liquid crystal sealing agent was evaluated. The detail of each measurement is shown below. The adhesive strength of the said liquid crystal sealing agent measured and evaluated two types of adhesive strength of (1) light and the thermosetting liquid crystal sealing agent, and (2) the adhesive strength of the thermosetting liquid crystal sealing agent. In addition, the display property of a liquid crystal display panel is a liquid crystal display produced only by (1) the display property of the liquid crystal display panel produced according to the normal method as a sample, (2) the display property of the liquid crystal display panel which attached the light shielding area, and (3) thermosetting. Three patterns of displayability of the panel were measured and evaluated.

[Viscosity Stability of Liquid Crystal Sealing Agent]

The viscosity value in 25 degreeC of the liquid crystal sealing agent was measured using the E-type viscosity meter. At the time of viscosity measurement, 100 mass parts of liquid crystal sealing agents were put into the container made from polyethylene, and it sealed, and it stored at 25 degreeC for 5 days. Subsequently, after a predetermined period, a viscosity value of 25 ° C. was measured with an E-type viscometer. And the change rate of the viscosity value in 25 degreeC / 5 days after the case where the viscosity value before sealing was made into 100 using the measured value was computed. At this time, when such a change rate is 20% or less, it is said that viscosity stability is high and it is favorable ((circle)), and when there exists a change exceeding 20%, it is poor viscosity stability and is bad ((x)), Viscosity stability was evaluated in two steps.

Adhesion Strength of Liquid Crystal Sealing Agent

1. Adhesive strength of light and thermosetting liquid crystal sealing agent

First, the liquid crystal sealing agent which added 1 mass% of 5 micrometers glass fibers was screen-printed the circular shape of diameter 1mm on the alkali free glass of 25 mm x 45 mm x thickness 5 mm. Next, the ultraviolet-ray of 100 mW / cm <2> is radiated using the ultraviolet irradiation apparatus (product of Ushio Electric Co., Ltd.) to the part which fixed the jig | tool after bonding the same glass paired with this board | substrate crosswise. It irradiated and hardened the liquid crystal sealing agent. At this time, the illuminance energy of the ultraviolet ray was 2000 mJ.

The test piece was produced by heat-processing the test piece which hardened the liquid crystal sealing agent with light at 120 degreeC, and 60 minutes using oven. Plane tensile strength of the finished specimen was measured by using a tensile tester (Model 210 Intesco Co., Ltd.) at a tensile speed of 2 mm / min and peeling in a direction parallel to the glass bottom. did. Here, the adhesive strength was evaluated in two stages according to the size of the plane tensile strength. That is, the case where the tensile strength became 10 MPa or more was said to be good adhesive strength ((circle)), and the case where the tensile strength became less than 10 Mpa was inferior to low adhesive strength (x).

2. Adhesive strength of thermosetting liquid crystal sealing agent

First, the liquid-crystal sealing agent which added 1 mass% of 5 micrometers glass fibers was screen-printed in circular shape of diameter 1mm on the alkali free glass of 25 mm x 45 mm x thickness 5 mm, and bonded and paired the same glass crosswise and fixed. . Next, the test piece was produced by heat-processing these two board | substrates bonded together 120 degreeC and 60 minutes using oven, and hardening a liquid crystal sealing agent only by thermosetting.

The planar tensile strength of the completed test piece was measured using the tensile tester (Model 210 Intesco Co., Ltd. product). Under the present circumstances, the measurement of the plane tensile strength and evaluation of the measurement result were made the same as the method demonstrated by the adhesive strength of the above-mentioned (A) light and the thermosetting liquid crystal sealing agent.

[Displayability of Liquid Crystal Display Panel]

1. Display of liquid crystal display panel manufactured by light and thermosetting

On the 40 mm x 45 mm glass substrate (RT-DM88PIN EHC Co., Ltd. product) which attached the transparent electrode and the oriented film, the line width of 0.5 mm and 50 micrometers was used using the liquid crystal sealing agent which added 1 mass% of glass fibers of 5 micrometers. A frame of 35 mm x 40 mm was drawn in thickness. The dispenser (shot master Musashi Engineering Co., Ltd. product) was used for drawing.

Next, the liquid crystal material (MLC-11900-000 Merck Co., Ltd. product) corresponded to the panel content amount after bonding board | substrates together was dripped precisely by the dispenser to the glass substrate paired with the board | substrate which formed the sealing pattern. Subsequently, under the reduced pressure of 90 Pa, two glass substrates were piled up so that a liquid crystal might be sealed, 100 degree-C / cm <2> ultraviolet-ray was irradiated using the ultraviolet irradiation device (made by Ushio Electric Co., Ltd.), and the liquid crystal sealing agent was hardened. At this time, the irradiation energy of ultraviolet rays was 2000 mJ. As a light source, a metal halide lamp was used. For the measurement of accumulated light quantity, the ultraviolet integrated photometer (UVR-T35 Topcon Co., Ltd. product) which has a measurement wavelength range of 300-390 nm and whose peak sensitivity wavelength is 365 nm was used. In addition, after hardening a liquid crystal sealing agent with light, the liquid crystal sealing agent was further hardened by heat-processing 120 degreeC for 60 minutes.

The deflection film was affixed on both surfaces of the two board | substrates bonded together, respectively, and it was set as the liquid crystal display panel. The liquid crystal display panel was driven by applying a voltage of 5 V to the liquid crystal display panel. At this time, it observed visually whether the liquid crystal display function near the chamber formed with the liquid crystal sealing agent functioned normally from the initial stage, and evaluated the display property of a liquid crystal display panel in two steps according to the predetermined | prescribed criterion. Here, the case where the liquid crystal display function is exhibited to the edge of a thread is said to be good displayability ((circle)), and when the display function is not exhibited to the place which is 0.3 mm or more away from the edge vicinity of a thread toward the inside of an edge. The display property was remarkably bad (×).

2. Display of liquid crystal display panel with light shielding area

On the 40 mm x 45 mm glass substrate (RT-DM88PIN ECH Co., Ltd. product) which attached the transparent electrode and the oriented film, 0.5 mm of line width and 50 micrometers were used using the liquid crystal sealing agent which added 1 mass% of 5 micrometers glass fibers. A frame of 35 mm x 40 mm was drawn in thickness. The dispenser (shot master Musashi Engineering Co., Ltd. product) was used for drawing.

Next, the liquid crystal material (MLC-11900-000 Merck Co., Ltd. product) corresponded to the panel content after bonding was dripped precisely with the dispenser. Subsequently, two glass substrates were piled up under the reduced pressure of 90 Pa, and the load was fixed under load, and the seal | sticker part of the board | substrate used as a front surface was coat | covered so that ultraviolet-ray might not be irradiated directly using aluminum tape. And the liquid crystal display panel which attached the light shielding area was produced by hardening a liquid crystal sealing agent with light and heat by the method similar to the measuring method of the said liquid crystal display panel.

The display function of the completed liquid crystal display panel mentioned above is "1. It measured and evaluated by the method similar to the "evaluation method of the displayability of the liquid crystal display panel produced by light and thermosetting." Here, since the criteria for evaluating the displayability of the liquid crystal display panel are as described above, a detailed description thereof will be omitted.

3. Displayability of Liquid Crystal Display Panel Made Only by Thermosetting

On the 40 mm x 45 mm glass substrate (RT-DM88PIN ECH Co., Ltd. product) which attached the transparent electrode and the oriented film, 0.5 mm of line width and 50 micrometers were used using the liquid crystal sealing agent which added 1 mass% of 5 micrometers glass fibers. A frame of 35 mm x 40 mm was drawn in thickness. The dispenser (shot master Musashi Engineering Co., Ltd. product) was used for drawing.

Next, the liquid crystal material (MLC-11900-000 Merck Co., Ltd. product) corresponded to the panel content after bonding was dripped precisely with the dispenser. Subsequently, two glass substrates were piled up under reduced pressure of 90 Pa, and it heated at 120 degreeC for 60 minutes using oven, and hardened the liquid-crystal sealing agent.

The deflection film was affixed on both surfaces of the two board | substrates bonded together, respectively, and it was set as the liquid crystal display panel. The liquid crystal display panel was driven by applying a voltage of 5 V to the liquid crystal display panel. At this time, it observed visually whether the liquid crystal display function near the chamber formed with the liquid crystal sealing agent functioned normally from the initial stage, and evaluated the display property of a liquid crystal display panel in two steps according to the predetermined | prescribed criterion. Here, since the criterion for evaluating the displayability of the liquid crystal display panel is the same as the method described above, the description is omitted.

Example 1

(e) 5 parts by mass of o-cresol novolac epoxy resin (manufactured by EOCN-1020-75 Nihon Kayaku Co., Ltd.) to 10 parts by mass of an epoxy ester (3000M Kyoeisha Chemical Co., Ltd. product) treated with high purity It melt | dissolved by heat and prepared the homogeneous solution. To this cooled solution, 1-hydroxycyclohexyl-phenyl-ketone (irgacure 184 chivas specialty chemical) which acts as an optical radical initiator as 52 parts by mass of compound A1 as (a) component and (c) component 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (manufactured by Amicure VDH-J Ajinomoto Fine Techno Co., Ltd.) 10 mass parts, (d) component, 20 mass parts of spherical silica (admafine A-802, product made by Admatex Co., Ltd.), (g) component, (gamma)-glycidoxy propyl trimethoxysilane ( 1 mass part of KBM 403 Shin-Etsu Chemical Co., Ltd. products were added, and it premixed with the mixer. Moreover, it knead | mixed until it became 5 micrometers or less in a triple roll, and it filtered with the mesh 10 micrometer filter (made by MSP-10-E10S ADVANTEC Co., Ltd.). The liquid crystal sealing agent (P1) was prepared by vacuum degassing the obtained filtrate.

[Example 2]

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

Example 3

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

Example 4

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

Example 5

24 mass parts of epoxy esters (3000M Kyoeisha Chemical Co., Ltd. product) which processed 5 mass parts of o-cresol novolak epoxy resins (EOCN-1020-75 Nihon Kayaku Co., Ltd. product) as a (e) component It melt | dissolved in the heat and prepared the homogeneous solution. To this cooled solution, 1-hydroxycyclohexyl-phenyl-ketone (irgacure 184 chivas specialty), which acts as an optical radical polymerization initiator as 20 parts by mass of Compound A2 and (c) component as (a) component 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Techno Co., Ltd. product) as 5 parts by mass of Chemicals Co., Ltd., and (b) component Γ-glycidoxypropyltrimethoxysilane as 15 parts by mass, (d) component, 30 parts by mass of spherical silica (manufactured by Admafine A-802 Admatex Co., Ltd.) and (g) other additives 1 mass part of phosphorus (KBM 403 Shin-Etsu Chemical Co., Ltd. product) was added, and it premixed by the mixer. Subsequently, after kneading until a solid raw material became 5 micrometers or less using a triple roll, the kneaded material was filtered by the mesh 10 micrometer filter (MSP-10-E10S ADVANTEC Co., Ltd. product). Liquid crystal sealing agent (P5) was prepared by vacuum degassing the obtained filtrate.

Example 6

As the component (e), 6 parts by mass of o-cresol novolac epoxy resin (manufactured by EOCN-1020-75 Nihon Kayaku Co., Ltd.) 6 parts by mass of a high-purity epoxy ester (3000M Kyoeisha Chemical Co., Ltd.) It melt | dissolved in the heat and prepared the homogeneous solution. 1-hydroxycyclohexyl which acts as an optical radical polymerization initiator as (a) component 9 mass parts of compound A2, 26 mass parts of compound A5, 26 mass parts of compound A6, and (c) component to this cooled solution. 2 mass parts of -phenyl- ketone (Irgacure 184 Chivas Specialty Chemicals Co., Ltd. product), and (b) component are 1, 3-bis (hydrazino carboethyl) -5-isopropyl hydantoin ( 10 parts by mass of Amcure VDH-J Ajinomoto Fine Techno Co., Ltd., (d) component, 14 parts by mass of spherical silica (admafine A-802, product of Admatex Co., Ltd.) and (g) component -1 mass part of glycidoxy propyl trimethoxysilane (made by KBM 403 Shin-Etsu Chemical Co., Ltd.) was added, and it premixed by the mixer. Subsequently, after kneading until the solid raw material became 5 micrometers or less using a triple roll, this kneaded material was filtered with the filter of 10 micrometers of mesh (made by MSP-10-E10S ADVANTEC Co., Ltd.). Liquid crystal sealing agent (P6) was prepared by vacuum degassing the obtained filtrate.

Example 7

As a component, 81 mass parts of compound A2 and (b) component are 1, 3-bis (hydrazino carboethyl) -5-isopropyl hydantoin (Amicure VDH-J Ajinomoto Fine Techno Co., Ltd.). Product) 10 mass parts, (d) component, and 8 mass parts of spherical silica (made by admafine A-802 admatex Co., Ltd.), and (g) component, gamma- glycidoxy propyl trimethoxysilane 1 mass part (KBM 403 Shin-Etsu Chemical Co., Ltd. product) was pre-mixed with the mixer. Subsequently, after kneading until the solid raw material became 5 micrometers or less using a triple roll, this kneaded material was filtered with the filter of 10 micrometers of mesh (made by MSP-10-E10S ADVANTEC Co., Ltd.). Liquid crystal sealing agent (P7) was prepared by vacuum degassing the obtained filtrate.

Example 8

As the component (e), 5 parts by mass of o-cresol novolac epoxy resin (manufactured by EOCN-1020-75 Nihon Kayaku Co., Ltd.) was treated with high-purity bisphenol A and EO adduct diacrylate (bis). It was made to melt | dissolve in 10 mass parts of coat # V700 Osaka Organic Chemical Industry Co., Ltd. products, and it was set as the homogeneous solution. To this cooled solution, 1-hydroxycyclohexyl-phenyl-ketone (irgacure 184 chivas specialty), which acts as an optical radical polymerization initiator as 52 parts by mass of Compound A7 and (c) component as (a) component 2 parts by mass of Chemicals Co., Ltd., (b) component, 10 parts by mass of adipic acid dihydrazide (manufactured by Amcure ADH Nippon Finechem Co., Ltd.), and (d) component, spherical silica (admapa) 1 mass part of (gamma)-glycidoxy propyl trimethoxysilane (KBM 403 Shin-Etsu Chemical Co., Ltd. product) is added as 20 mass parts of phosphorus A-802 admatex Co., Ltd. products, and (g) component, and a mixer Premixed. Subsequently, after kneading until the solid raw material became 5 micrometers or less using a triple roll, this kneaded material was filtered with the filter of 10 micrometers of mesh (made by MSP-10-E10S ADVANTEC Co., Ltd.). The liquid crystal sealing agent (P8) was prepared by vacuum degassing the obtained filtrate.

Example 9

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

Example 10

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

Example 11

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

Example 12

As the component (e), 15 parts by mass of o-cresol novolac epoxy resin (manufactured by EOCN-1020-75 Nihon Kayaku Co., Ltd.) was treated with high-purity bisphenol A and EO adduct diacrylate (biscote # V700 Osaka organic). It melt | dissolved in 22 mass parts of Chemical Industry Co., Ltd. products, and it was made into a homogeneous solution, and further cooled. 1-hydroxy-cyclohexyl-phenyl-ketone (irgacure 184 chivas specialty chemicals) which acts as a photoradical initiator as 20 mass parts of compound A7 and (c) component to a cooled solution as (a) component (Product) 2 mass parts, (b) component, 15 mass parts of adipic acid dihydrazide (made by Amcure ADH Nippon Finechem Co., Ltd.), and (d) component are spherical silica (admafine A) -802 admatex Co., Ltd.) 25 mass parts and (g) component, add 1 mass part of (gamma)-glycidoxy propyl trimethoxysilane (KBM 403 Shin-Etsu Chemical Co., Ltd. product), and prepare with a mixer. Mixed. Subsequently, after kneading until the solid raw material became 5 micrometers or less using a triple roll, this kneaded material was filtered with the filter of 10 micrometers of mesh (made by MSP-10-E10S ADVANTEC Co., Ltd.). Liquid crystal sealing agent (P12) was prepared by vacuum degassing the obtained filtrate.

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

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

[Comparative Example 4]

As a component (a), 62 mass parts of epoxy ester 3000M was used instead of the compound A1 and epoxy ester 3000M used in Example 1, and liquid crystal sealing agent (Q4) was prepared like Example 1.

[Comparative Example 5]

As the component (a), 52 parts by mass of the compound C1 synthesized by the following synthesis method instead of the compound A7 was used in the same manner as in Example 8 to prepare a liquid crystal sealing agent (Q5).

[Synthesis of Compound C1]

In a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol A epoxy resin (manufactured by Epikron 850CRP, Dainippon Ink and Chemicals Co., Ltd.), 43 g of methacrylic acid, and a triethanolamine 0.2 as a catalyst 0.2 g of hydroquinone monomethyl ethers were mixed as g and a polymerization inhibitor, and the compound C1 was obtained by heating and stirring a mixture for 110 hours and 5 hours, blowing dry air. 12 times of washing | cleaning processes were repeated with the ultrapure water about this obtained compound C1. HPLC and NMR analysis of the compound C1 confirmed that 50% of the epoxy groups were methacryloyl-modified bisphenol A epoxy resins. In addition, the number average molecular weight was 426 as a result of FD-MS analysis of compound C1.

[Comparative Example 6]

As a component (a), 52 mass parts of compound C2 synthesize | combined by the following synthesis method instead of compound A7 was used, and all liquid crystal sealing agents (Q6) were prepared like Example 8.

[Synthesis of Compound C2]

In a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol A epoxy resin (manufactured by Epikron 850CRP, Dainippon Ink and Chemicals), 37 g of acrylic acid, 0.2 g of triethanolamine as a catalyst, 0.2 g of hydroquinone monomethyl ether was mixed as a polymerization inhibitor. The mixture was heated and stirred at 110 degreeC for 12 hours, blowing in air, and compound C2 was obtained. Washing | cleaning process was repeated 12 times with ultrapure water about the obtained compound C2. HPLC and NMR analysis of the compound C2 confirmed that 50% of the epoxy groups were acryloyl-modified bisphenol A epoxy resins. In addition, the number average molecular weight was 412 as a result of FD-MS analysis of compound C2.

Comparative Example 7

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

Comparative Example 8

Except having used 52 mass parts of epoxy esters (3000A Kyoeisha Chemical Co., Ltd.) which is a diacrylate of the bisphenol-A epoxy resin instead of the compound A7 used in Example 8, it carried out similarly to Example 8, and all liquid-crystal sealing agents (Q8) was prepared.

Each evaluation result by the liquid crystal sealing agent obtained in Examples 1-12 and Comparative Examples 1-8 is put together in Table 1, 2, and is shown.

As shown in Table 1, 2, the liquid-crystal sealing agent to which liquid crystal sealing agents P1-P12 which concerns on this invention were applied has said viscosity stability, adhesive strength, and the display property of the yarn vicinity of the liquid crystal display panel using the same, and the seal of a light shielding area. Good evaluation results were confirmed in each item of display in the vicinity. Moreover, when hardening such a liquid crystal sealing agent only by heat, it was confirmed that adhesive strength is high and it is excellent in the display property of a liquid crystal display panel.

On the other hand, although it is a compound which has both a (meth) acryl group and an epoxy group like Comparative Examples 1-6, the liquid crystal sealing agent which used the compound whose number average molecular weight is less than 500 as a raw material is all low in viscosity stability, Since the display nonuniformity of the liquid crystal generate | occur | produced in the vicinity of the room, it was confirmed that displayability was low and it was inferior to each Example. In addition, as in Comparative Examples 4 and 8, it was confirmed that all of the liquid crystal sealing agents made of a methacrylated epoxy resin different from the structure of the present invention were both low in viscosity stability and adhesive strength and remarkably inferior.

The liquid crystal sealing agent of this invention is favorable for high viscosity stability and sclerosis | hardenability. Therefore, since the line width of a sealing pattern becomes thinner or the possibility of replacing the liquid crystal sealing agent with the apparatus, such as a dispenser, increases the number of times, it is suppressed low, and it can manufacture, aiming at shortening the hardening time of a liquid crystal display panel by increasing a yield. . Moreover, since such liquid crystal sealing agent is suppressed low solubility with respect to a liquid crystal, it is suitable for the liquid crystal dropping system.

This application claims priority based on the application numbers JP2006-243057, JP2006-243059, filed September 7, 2006, and the application numbers JP2006-350198, JP2006-350317, filed December 26, 2006. All the content described in these application specification is integrated in this specification.

Claims (8)

(a) A compound which has a (meth) acryloyl group and glycidyl group in a molecule | numerator, and a number average molecular weight is 500-2000,
(b) a thermal latent curing agent,
(c) radical polymerization initiator, and
(d) filler
Including,
Liquid crystal sealing agent whose said (a) component is a compound represented by following formula (I).
[Formula I]

[In Formula (I),
R ₁₁ to R ₁₆ each independently represent a hydrogen atom or a methyl group, provided that both R ₁₃ and R ₁₄ are not methyl groups, and both R ₁₅ and R ₁₆ are not methyl groups;
X ₁₁ and X ₁₂ each independently represent an alkylene group having 1 to 10 carbon atoms or a group represented by the following general formula (I-1);
X ₁₃ and X ₁₄ each represent a C1-C10 alkylene group, and the other represents a group represented by the following general formula (I-2);
A represents a group represented by the following formulas (I-3a), (I-3b) or (I-3c);
P each 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, m represents an integer of 0 to 4, where a + b + c + d + m = 6 And not all of a, b and c are zero;
j represents an integer of 0 or 1, k and l represent an integer of 0 to 10, respectively.]
[Formula I-1]

[In Formula I-1
Y ₂₁ and Y ₂₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₂₁ is bonded to O of the acryloyl group of the formula (I),
n represents an integer of 1 to 10]
[Formula I-2]

[In the above formula (I-2),
Y ₃₁ and Y ₃₂ each independently represent an alkylene group having 1 to 10 carbon atoms,
Y ₃₂ is bonded to O of the acryloyl group of the formula (I)]
[Formula I-3a]

[In 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,
Z represents a single bond, -O- group, -S- group, -SO ₂ -group, -C (R ₄₃ ) (R ₄₄ )-group or a group represented by the following formula t1, wherein R ₄₃ and R ₄₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group,
r and s each independently represent an integer of 0 to 4]
[Formula t1]

[Formula I-3b]

[In 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]
[Formula I-3c]

[In 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 method of claim 1,
The liquid crystal sealing agent whose compound represented by the said general formula (I) is 1 or more types of compound which has 1 or more acryloyl group, methacryloyl group, and an epoxy group together in a molecule | numerator. The method of claim 1,
The liquid crystal sealing agent which further contains either (e) epoxy resin or (f) acrylic compound. The method of claim 1,
Liquid crystal sealing agent whose said (c) component is an optical radical polymerization initiator. The method of claim 1,
Liquid crystal sealing agent whose said (c) component is a thermal radical polymerization initiator. The method of claim 1,
The liquid crystal sealing agent whose content of the said (a) component is 5-90 mass parts with respect to 100 mass parts of liquid crystal sealing agents. In the manufacturing method of the liquid crystal display panel manufactured by bonding the two board | substrates which oppose through a liquid crystal sealing agent,
Preparing one or more substrates having an edge-shaped display region formed such that the pixel array region is surrounded by the liquid crystal sealing agent according to claim 1,
Dropping a liquid crystal in the display region in an uncured state or on the other substrate;
Stacking the substrate on which the liquid crystal is dropped and the other substrate; and
The two substrates A step of applying either light and heat or light or heat to the liquid crystal sealing agent sandwiched therebetween
Method of manufacturing a liquid crystal display panel comprising a. The liquid crystal display panel obtained by the manufacturing method of the liquid crystal display panel of Claim 7.