JP2007219039A - Sealant composition for liquid crystal display cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealant composition for liquid crystal display cells which suppresses contamination of a liquid crystal by a raw resin component, etc., in heat curing and ensures excellent properties of a cured product. <P>SOLUTION: The sealant composition for liquid crystal display cells contains, as essential components, (A) a phenol aralkyl type epoxy resin, (B) a reaction mixture obtained by reacting an epoxy resin with (meth)acrylic acid and having an unmodified epoxy resin content of 0-5 mass%, (C) a latent curing agent, (D) a photopolymerization initiator and (E) an inorganic filler. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sealing agent composition for a liquid crystal display cell that suppresses contamination to liquid crystal, and in particular, in a shaded portion that is not exposed to UV irradiation light, contamination from the sealing agent to liquid crystal during heat curing after light irradiation. It is related with the sealing compound composition for liquid crystal display cells which suppressed the property.

  Until now, the manufacturing method of the liquid crystal display cell has been applied in such a state that a sealing agent is applied to the TFT side substrate by screen printing or a dispenser device, and then the color filter side substrate sprayed with a bead-like spacer agent is overlapped. Under pressure, the sealing agent is heated and cured to produce an empty panel. Furthermore, since the liquid crystal display cell is manufactured by cutting the empty panel with a scribing device and then injecting the liquid crystal from the injection port under reduced pressure, it takes time to inject the liquid crystal. In addition, there is a technical problem that the proportion of the liquid crystal injection time increases by increasing the substrate size and reducing the panel gap in order to reduce the response speed of the liquid crystal, resulting in a decrease in productivity and liquid crystal display. It was difficult to reduce the cost of the apparatus.

  However, in recent years, there has been a strong demand for cost reduction of large panels, and a method for manufacturing a liquid crystal display device using a liquid crystal dropping method has been studied. In the conventional method, the liquid crystal that has not come into contact with the uncured sealant composition comes into contact, and the contamination of the sealant composition with respect to the liquid crystal has emerged as an important problem. The liquid crystal dropping system is a color filter side substrate or a photomask in which a sealing agent is applied to a TFT side substrate by screen printing or a dispenser device, then liquid crystal is applied by a dispenser device, and a bead-like spacer agent is dispersed. In this method, the color filter side substrates on which spacers are formed are bonded together (Japanese Patent No. 2846842: Patent Document 1).

  In a conventional liquid crystal dropping type sealant, it has been proposed to use a main agent obtained by partial (meth) acrylate conversion of a bisphenol A type epoxy resin (Japanese Patent Laid-Open No. 2001-133794: Patent Document 2). However, generally used liquid epoxy resins (bisphenol A type, bisphenol F type, phenol novolac type) have a close SP value (solubility parameter value) with liquid crystal and tend to be easily dissolved.

  On the other hand, by narrowing the frame to increase the display screen size with respect to the panel size, the liquid crystal and sealant interface part that was previously hidden in the BM part (black matrix) becomes narrower, resulting in liquid crystal contamination from the sealant. There has been a problem that orientation abnormalities, display unevenness and the like are easily visible. Furthermore, since the number of electrode patterns associated with the arrangement of electrode patterns and high-definition painting increases, the proportion of shaded portions where the sealing agent is not irradiated with ultraviolet rays increases. Therefore, there is a problem that unreacted raw material epoxy resin or the like contaminates the liquid crystal.

  Then, the method of controlling the content rate of the hydrogen bondable functional group of a raw material epoxy resin is proposed for the purpose of improving the contamination | pollution property of a shadow part (Unexamined-Japanese-Patent No. 2004-163766: patent document 3). However, the raw material epoxy resin used (in the phenol novolac resin) remains unreacted raw material epoxy resin even after partial (meth) acryl modification, and includes a binuclear component. Therefore, it dissolves in the liquid crystal during heat curing.

  Furthermore, a method for suppressing solubility in liquid crystals by introducing one alcoholic hydroxyl group per molecule of epoxy resin has been proposed (Japanese Patent Laid-Open No. 2004-244515: Patent Document 4). However, although this method uses resorcinol as a raw material epoxy resin and oligomerizes the hydroxyl group in the molecule, it has a problem that the crosslinking density is low and the heat resistance of the cured product is poor.

  For the reasons described above, the liquid crystal dropping type photothermal curing combined type liquid crystal sealant that has been proposed in the past is difficult to balance the contamination of the shadowed portion of the liquid crystal during thermal curing with the properties of the cured product. It has become.

Japanese Patent No. 2846842 JP 2001-133794 A JP 2004-163766 A JP 2004-244515 A

  The present invention has been made in view of the above circumstances, and has been required for a conventional sealing agent composition for a liquid crystal display cell. An object of the present invention is to provide an excellent sealing agent composition for liquid crystal display cells.

  As a result of intensive studies to achieve the above object, the present inventors have found that the molecular weight of the epoxy resin used in the sealing agent is small and the SP value of the liquid crystal and the sealing material is close as a cause of contamination. Therefore, it has been found that there is a problem in that the raw material epoxy resin, which is a component of the sealing agent, dissolves in the liquid crystal due to the lower viscosity of the sealing agent during heating. Therefore, the use of liquid epoxy resin with low solubility in liquid crystal, preferably using rubber-like polymer fine particles with pseudo-curing property, can suppress the decrease in viscosity of the sealant, and the contamination property to liquid crystal. The present inventors have found that a sealing agent composition for liquid crystal display cells with a low content can be obtained, and have made the present invention.

（式中、Ｇはグリシジル基を表す。ｎは１〜５の整数を表す。）
で表され、ｎ≧３である成分の割合が１０質量％以下のものである（１）記載のシール剤組成物。
（３）（Ｂ）成分のエポキシ樹脂が、ビスフェノール型エポキシ樹脂である（１）又は（２）に記載のシール剤組成物。
（４）（Ｂ）成分の反応混合物が、未反応のエポキシ樹脂０〜５質量％、部分（メタ）アクリレート変性エポキシ化合物０〜３０質量％、全（メタ）アクリレート変性化合物７０〜１００質量％の割合で混合されていることを特徴とする（１）〜（３）のいずれかに記載の液晶表示セル用シール剤組成物。
（５）更に、（Ｆ）１００℃以下の温度範囲で擬似硬化性を示すゴム状ポリマー微粒子を含有することを特徴とする（１）〜（４）のいずれかに記載の液晶表示セル用シール剤組成物。 Therefore, this invention provides the sealing compound composition for liquid crystal display cells shown below.
(1) (A) a phenol aralkyl type epoxy resin,
(B) a reaction mixture obtained by reacting (meth) acrylic acid with an epoxy resin, wherein the content of the unmodified epoxy resin is 0 to 5% by mass;
(C) a latent curing agent,
(D) a photopolymerization initiator,
(E) A sealing agent composition for liquid crystal display cells, comprising an inorganic filler as an essential component.
(2) The phenol aralkyl type epoxy resin in component (A) is represented by the following general formula (1)

(In the formula, G represents a glycidyl group. N represents an integer of 1 to 5.)
The sealant composition according to (1), wherein the ratio of the component represented by the formula n ≧ 3 is 10% by mass or less.
(3) The sealing agent composition according to (1) or (2), wherein the epoxy resin as the component (B) is a bisphenol type epoxy resin.
(4) The reaction mixture of the component (B) is 0 to 5% by mass of an unreacted epoxy resin, 0 to 30% by mass of a partially (meth) acrylate-modified epoxy compound, and 70 to 100% by mass of a total (meth) acrylate-modified compound. The sealing agent composition for liquid crystal display cells according to any one of (1) to (3), wherein the composition is mixed at a ratio.
(5) The liquid crystal display cell seal according to any one of (1) to (4), further comprising (F) rubber-like polymer fine particles exhibiting pseudo-curability in a temperature range of 100 ° C. or lower. Agent composition.

  According to the present invention, by using a phenol aralkyl type epoxy resin, more preferably by using rubbery polymer fine particles exhibiting pseudo-curing property in a temperature range of 100 ° C. or less, even in a shaded portion that is difficult to be irradiated with UV, It is possible to provide a sealing agent composition for a liquid crystal display cell, which suppresses dissolution of the sealing agent constituents from the sealing agent to the liquid crystal during thermosetting and is excellent in non-contamination to the liquid crystal.

（式中、Ｇはグリシジル基を表す。ｎは１〜５の整数を表す。）
で表され、分子内に２個以上のエポキシ基を有し、上記式で表されるエポキシ樹脂の繰り返し単位数を示すｎが１〜５の範囲内のものが好適であり、より好ましくはｎ≧３である成分の割合がゲル浸透クロマトグラフ（ＧＰＣ：検出器ＵＶ２５４ｎｍ）において１０質量％以下、特に５質量％以下であるエポキシ樹脂である。 Hereinafter, embodiments of the present invention will be described.
[(A) Phenol aralkyl type epoxy resin]
The phenol aralkyl type epoxy resin used in the present invention has the following general formula (1):

(In the formula, G represents a glycidyl group. N represents an integer of 1 to 5.)
It is preferable that n has a number of repeating units of the epoxy resin represented by the above formula, and n is in the range of 1 to 5, more preferably n. It is an epoxy resin in which the proportion of the component ≧ 3 is 10% by mass or less, particularly 5% by mass or less in gel permeation chromatograph (GPC: detector UV254 nm).

  Such an epoxy resin can be obtained by reacting a phenol aralkyl type phenol resin represented by the following formula (2) with a large excess of epichlorohydrin. The usage-amount of epichlorohydrin is 1-15 mol normally with respect to 1 equivalent of hydroxyl groups in a phenol resin, Preferably it is 5-10 mol.

（式中、ｍは繰り返し数を表し、通常１〜５の整数である。）

(In the formula, m represents the number of repetitions and is usually an integer of 1 to 5.)

  Here, the synthesis of the phenol aralkyl type phenol resin (formula (2)), which is a precursor of the epoxy resin of the present invention, involves reacting a large excess of phenol with p-xylene diol in the presence of an acid catalyst or a basic catalyst. Can be obtained at In this case, the usage-amount of phenol is 2-30 mol normally with respect to 1 mol of p-xylenediol, Preferably it is 10-20 mol.

  Alternatively, the phenol aralkyl type epoxy resin obtained by the usual synthesis method is dissolved in a solvent such as toluene or methyl isobutyl ketone, and then a poor solvent such as hexane is dropped, and the component having a high molecular weight by the reprecipitation method is added. It can be obtained by separating and removing.

  The epoxy resin used in the present invention contains epichlorohydrin in a small amount because it uses epichlorohydrin in the synthesis process, but the amount of hydrolyzable chlorine is 600 ppm or less, more preferably 300 ppm or less. It is preferable. When the amount of hydrolyzable chlorine is more than 600 ppm, the contamination of the liquid crystal may be a problem. The amount of hydrolyzable chlorine is, for example, about 0.5 g of epoxy resin dissolved in 20 ml of dioxane, or the same amount of ion-exchanged water is added to the epoxy resin, and extracted at 100 ° C. for 20 hours. , After refluxing for 3 hours with 5 ml of 1N KOH / ethanol solution having a chlorine concentration in water, titration with 0.01N silver nitrate solution can be used for quantification.

[(B) Reaction mixture obtained by reacting (meth) acrylic acid with epoxy resin]
The component (B) used in the present invention is obtained by reacting an epoxy resin with (meth) acrylic acid.

  The epoxy resin may be a bifunctional or higher functional epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, cresol novolak type. An epoxy resin etc. are mentioned. Of these, bisphenol-type epoxy resins that are liquid at room temperature are preferred.

  As a reaction ratio of such an epoxy resin and (meth) acrylic acid, the molar ratio of (meth) acryloyl group of (meth) acrylic acid and epoxy group of epoxy resin ([(meth) acryloyl group / epoxy group] × 100) = 70 to 100% of the reaction is preferable, and more preferably 80 to 100% of the reaction is used. When the proportion of (meth) acrylic acid is less than 70%, there is a possibility that an unreacted epoxy resin may remain, which may cause a problem in the contamination property to the liquid crystal.

  The above reaction is usually preferably carried out in an organic solvent such as toluene. Further, it is preferable to use an addition reaction catalyst such as triphenylphosphine, triethylamine, triethanolamine or the like. These blending amounts are not particularly limited. Moreover, although the said reaction can be performed according to a conventional method, as reaction conditions, it is preferable to set it as 3 to 24 hours at 80-110 degreeC.

を示し、「アクリロキシ基」はＣＨ₂＝ＣＨＣＯＯ−（アクリロイロキシ基）を、「メタクリロキシ基」はＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ−（メタクリロイロキシ基）を示す。 In the present invention, (meth) acrylic acid represents acrylic acid or methacrylic acid, and (meth) acrylate represents acrylate or methacrylate.
In addition, the “glycidyl group”

“Acryloxy group” represents CH ₂ ═CHCOO— (acryloyloxy group), and “methacryloxy group” represents CH ₂ ═C (CH ₃ ) COO— (methacryloyloxy group).

By the above reaction, a partial (meth) acrylate-modified epoxy compound in which a part of the epoxy group of the epoxy resin is modified to a group represented by the following general formula (3), and all the epoxy groups of the epoxy resin are represented by the following general formula The (meth) acrylate modified compound modified to the group represented by (3) is produced, and usually these are the unreacted epoxy resin, the partial (meth) acrylate modified epoxy compound, and the (meth) acrylate modified. Present as a mixture with the compound.

と表した場合、これを（メタ）アクリル酸
ＣＨ₂＝ＣＲ−ＣＯＯＨ（ＲはＨ又はＣＨ₃）
と反応させると、未反応のエポキシ樹脂（ｉ）と、下記式

で示されるエポキシ樹脂の一部のエポキシ基が開環した部分（メタ）アクリレート変性エポキシ化合物（ｉｉ）と、下記式

で示されるエポキシ樹脂の全部のエポキシ基が開環した（メタ）アクリレート変性化合物（ｉｉｉ）が得られる。
従って、上記式（３）の基は、

として存在する。 That is, for example, epoxy resin

And (meth) acrylic acid CH ₂ = CR-COOH (R is H or CH ₃ )
When reacted with unreacted epoxy resin (i), the following formula

A part (meth) acrylate modified epoxy compound (ii) in which a part of the epoxy group of the epoxy resin represented by

A (meth) acrylate-modified compound (iii) in which all the epoxy groups of the epoxy resin represented by the above formula are opened is obtained.
Therefore, the group of the above formula (3) is

Exists as.

  Unreacted epoxy resin present in the above reaction mixture, partially (meth) acrylate-modified epoxy compound in which a part of the epoxy group of the epoxy resin is modified, and all of the epoxy groups of the epoxy resin are modified (meth) As a mixing ratio of the acrylate-modified compound, the unreacted epoxy resin is 0 to 5 mass%, particularly 0 to 2 mass%, the partial (meth) acrylate-modified epoxy compound is 0 to 30 mass%, particularly 0 to 20 mass%, It is preferable that all (meth) acrylate-modified compounds are mixed in an amount of 70 to 100% by mass, particularly 80 to 100% by mass.

  The blending amount of the component (B) is preferably 100 to 250 parts by mass, particularly 150 to 200 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of the component (B) is too large, an adhesive force at the time of photocuring can be obtained, but there is a possibility that characteristics (increase in shrinkage and moisture permeability) in subsequent thermosetting may be reduced. When there is too little, the crosslinking density at the time of photocuring will fall. As a result, the adhesive force in the temporary fixing process is reduced, and the glass substrate may be peeled off due to impact or glass deflection during conveyance of the glass substrate.

[(C) Latent curing agent]
The latent curing agent used in the sealant composition for liquid crystal display cells of the present invention is solid at room temperature, and liquefies during heat curing to act as a curing agent for the epoxy resin.

  Examples of this component include dicyandiamide, carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, iminodiacetic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide diacid Hydrazide, hexadecanedihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydradiide 1,4-naphthoic acid dihydrazide, Amicure VDH, Amicure UDH (trade name, manufactured by Ajinomoto Co., Inc.), citric acid Organic acid hydrazides such as hydrazide. These can be used singly or in combination of two or more. Among these, Amicure VDH and Amicure UDH represented by the following formula can be preferably used because they have a relatively low melting point and an excellent balance of curability.

Amicure VDH
(1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin)

Amicure UDH
(7,11-octadecadien-1,18-dicarbohydrazide)

  The latent curing agent has an average particle size of 0.1 to 2 μm, more preferably 0.5 to 1.5 μm, and a particle size of 90% by mass when accumulated is 3 μm or less, particularly 2.5 μm or less. It is preferable to use one. In addition, the average particle diameter here and the particle diameter at the time of 90 mass% accumulation are the values measured with the particle size distribution measuring device (Microtrac MT3000: Nikkiso Co., Ltd. product) based on the laser diffraction scattering method.

  Here, since the latent curing agent is a solid at room temperature, in the use thereof, a wet pulverized and classified by a device such as a bead mill, an attritor or a ball mill is used as a pretreatment, and further three It is preferable to disperse and knead with a roll or the like so that the average particle size and the particle size when 90% by mass are accumulated, and more preferably no particle size of 3 μm or more.

In this case, it is preferable to use a product obtained by mixing a part or all of the latent curing agent with a silane coupling agent represented by the following general formula (4) and treating the mixture with a wet bead mill.
R ¹ C ₃ H ₆ SiR ² _n (OR ³ ) _3-n (4)
(In the formula, R ¹ is a glycidoxy group, an acryloxy group or a methacryloxy group. R ² and R ³ are alkyl groups, and n is 0, 1 or 2.)

Here, the alkyl group of R ² preferably has 1 or 2 carbon atoms, and the alkyl group of R ³ preferably has 1 or 2 carbon atoms.

  Examples of silane coupling agents used for surface treatment of such latent curing agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxy. Propyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane , Γ-acryloxypropyltriethoxysilane and the like. These can be used singly or in combination of two or more. Among these, γ-glycidoxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like can be preferably used from the viewpoint of further improving the potential.

  When using the said silane coupling agent, the usage-amount is about 0.1-6 mass% normally with respect to a latent hardening | curing agent, It is preferable to add in the range of 1-3 mass% especially. If the amount added is too small, the surface treatment may not be sufficiently performed, and the pot life may be deteriorated. On the other hand, if the amount is too large, the liquid crystal may be contaminated.

  In addition, although it does not specifically limit about the apparatus used when surface-treating a latent hardening | curing agent with a silane coupling agent, A Henschel mixer, a ball mill, a bead mill etc. are mentioned, Even if it processes by any method of dry or wet Good.

  The wet bead mill is not particularly limited as long as it has a rotor for creating a shearing field in a container for treating a slurry solution containing a curing agent and beads moving in the shearing field. Continuously equipped with a pump mechanism capable of repeatedly processing a slurry containing a curing agent, and a separator mechanism that prevents beads from flowing out when the resin is discharged. A system type is preferable. As such a bead mill, SC-MILL (SC100) manufactured by Mitsui Mining Co., Ltd. can be used. The beads to be used are not limited, but those made of zirconia, alumina, glass, steel with a diameter of 0.25 to 1.5 mm can be used according to the material and fraction of the curing agent, and the processing chamber is effective. It is preferable to fill 60 to 90% by volume of the volume, more preferably 80 to 85% by volume. In the case of a continuous wet bead mill equipped with a separator mechanism, the viscosity of the slurry containing the curing agent (25) is adjusted by adjusting the processing temperature, the blending amount of the curing agent, and the processing flow rate in order to smoothly perform the repeated processing. (° C.) is preferably 50 Pa · s or less.

  The compounding ratio of this latent curing agent is an active hydrogen equivalent, and 0.7 to 2.0 equivalents with respect to the total amount of the (A) component phenol aralkyl epoxy resin component and the (B) component epoxy component. Preferably, it is 0.8-1.5 equivalent. If the amount is too large, unreacted curing agent remains, which may affect moisture resistance. On the other hand, if the amount is too small, unreacted / uncured epoxy resin remains, which may cause deterioration of the liquid crystal contamination and cured product properties (glass transition temperature, adhesive strength).

[(D) Photopolymerization initiator]
As the photopolymerization initiator, all conventionally known photopolymerization initiators used for photopolymerization of (meth) acrylic groups can be used.

  Specific examples of the photopolymerization initiator component include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 1-phenyl-2-hydroxy-2. -Methylpropan-1-one, benzophenone, 1- {4- (2-hydroxyethoxy) -phenyl} -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 {4- ( Methylthio) phenyl} -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, oligo (2-hydroxy-2-methyl-1- ( 4- (1-methylvinyl) phenyl) propanone (trade name: ESACURE KIP-150, manufactured by LAMBERTI SpA), IRGACUR Phenyl ketones such as E 2959 (trade name, manufactured by Ciba Specialty Chemicals), IRGACURE 127 (trade name, manufactured by Ciba Specialty Chemicals), Adeka optomer N-1414, Adeka optomer N -1717 (trade name, manufactured by Asahi Denka Co., Ltd.), IRGACURE OXE01, IRGACURE OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRGACURE 754 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, (2,4,6-trimethylbenzoyl) Diphenylphosphine oxa Examples thereof include benzoylphosphine oxides such as id, etc. These can be used alone or in combination of two or more.

  Among the above examples, especially for liquid crystal display cells, ESACURE KIP-150 (manufactured by LAMBERTI SpA), IRGACURE 127, IRGACURE 2959, from the point of low VOC (volatile organic compound) during photocuring. IRGACURE 754 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is suitable.

  The blending amount of the present photopolymerization initiator component is 0.1 to 6% by mass, preferably 1 to 5% by mass, more preferably 2 to 4% by mass with respect to the total amount of the above component (A) and component (B). It is preferable to add in the range. If the addition amount is too small, the photopolymerizability / curability may be lowered, and conversely if it is too much, the preservability and workability of the sealing agent composition may tend to be lowered. Furthermore, problems such as contamination of the liquid crystal due to the decomposition component of the photopolymerization initiator and uneven alignment are likely to occur.

[(E) Inorganic filler]
Various known inorganic fillers can be added to the sealant composition for liquid crystal display cells of the present invention in order to reduce the expansion coefficient.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, titanium oxide, silica titania, boron nitride, aluminum nitride, silicon nitride, magnesia, magnesium silicate, talc, mica, and the like. However, two or more types can be used in combination. Of these, silica, alumina and talc are preferably used alone or in combination of two or more.

  The inorganic filler used preferably has a particle size of 3 μm or more and 1% by mass or less and an average particle size of 0.1 to 2 μm. Here, when the content rate with a particle size of 3 μm or more exceeds 1% by mass, the accuracy of gap-out of the glass substrate is deteriorated, and the bonding may be difficult. On the other hand, if the average particle size is less than 0.1 μm, the viscosity increases, the coating amount from the needle decreases, the coating speed decreases, and the productivity may deteriorate, which is not practical. The average particle size is a value measured by a particle size distribution measuring apparatus based on the laser diffraction scattering method.

  The content of the inorganic filler in the sealing agent composition for liquid crystal display cells of the present invention is preferably 10 to 30% by mass, more preferably 15 to 25% by mass. When the content is less than 10% by mass, since the expansion coefficient is large, there is a tendency to cause distortion after curing. When it exceeds 30% by mass, the viscosity of the composition becomes high, so that the dispersibility of the spacer agent to be added after use and the gap-out accuracy of the glass substrate may be deteriorated.

  It is preferable to use the inorganic filler that has been surface-treated with a coupling agent described later, such as a silane coupling agent or a titanium coupling agent. More preferably, the epoxy resin to be used and the filler surface-treated with a coupling agent are preliminarily decompressed and kneaded. Thereby, the interface between the filler surface and the epoxy resin can be well wetted, and the moisture resistance reliability is remarkably improved.

[(F) Rubber-like polymer fine particles showing pseudo-curability]
The rubber-like polymer fine particles exhibiting pseudo curability used in the sealant composition for liquid crystal display cells of the present invention exhibit pseudo curability in a temperature range of 100 ° C. or lower. Here, the pseudo-curing property means that as the particles swell, the viscosity increases and exhibits pseudoplastic flow. Specifically, as the pseudo-curing rubber-like polymer fine particles, specifically, silicone rubber fine particles, silicone resin Fine particles, polyethylene fine particles, polypropylene fine particles, polyvinyl chloride fine particles, polymethyl methacrylate fine particles, crosslinked polymethyl methacrylate fine particles, poly n-butyl acrylate fine particles and other polyacrylate-based fine particles, crosslinked polystyrene fine particles, nylon 12 fine particles, melamine resin fine particles, benzoguanamine Resin particles, melamine-guanamine resin particles, polyurethane resin particles, polyvinyl acetate particles, polystyrene-vinyl acetate copolymer particles, polyester particles, urea resin particles, phenol resin particles, epoxy resin particles Rubbery polymer fine particle surface in the epoxy resin, the acrylic resin include those obtained by introducing a functional group that is easily to cause a urethane resin or the like and swelling gelation.

  In this case, examples of the functional group include a carboxyl group. As a method for introducing the functional group, a linear polymer having a carboxyl group is chemically grafted (bonded) to the core particle. Obtainable.

  The pseudo-curing rubber-like polymer fine particles preferably have a primary particle diameter of 0.1 to 1 μm, particularly 0.1 to 0.6 μm, as measured by a laser diffraction scattering method. The average aggregate (secondary) particle size is preferably 2 to 20 μm. If the secondary particle size is too large, the gap controllability at the time of bonding may be deteriorated. Among these pseudo-curing rubber-like polymer fine particles, in particular, core-shell type acrylic fine particles (a core portion made of a (meth) acrylate polymer having a glass transition temperature of −30 ° C. or lower and a glass transition temperature of 70 ° C. or higher ( Partially cross-linked acrylic fine particles having a core-shell structure in which the shell portion of the shell portion of the (meth) acrylate-based polymer is ion-crosslinked are further preferable because they have higher adhesive strength and are effective in preventing seepage.

  Specific examples of such partially crosslinked acrylic fine particles having a core-shell structure include Zefiac F351 (manufactured by Zeon Kasei Co., Ltd.).

  The addition amount of the pseudo-curing rubber-like polymer fine particles as described above is 3 with respect to the total amount of the (A) component phenol aralkyl epoxy resin and the (B) component reaction mixture from the standpoint of preventing bleeding. The range of -30 mass% is preferable. More preferably, it is the range of 5-20 mass%. If it is less than 3% by mass, it is difficult to be in a B-stage state, the effect of preventing the diffusion of the raw material resin into the liquid crystal is not seen, and the orientation may deteriorate. Moreover, when it exceeds 30 mass%, there exists a possibility that a viscosity may become high and problems, such as dispensing property and gap controllability, may come out. In addition, when mixing the pseudo-curable fine particles, in order to prevent the problem of poor gap control due to the agglomerates, the agglomerates are preliminarily mixed with the filler or premixed with the resin used, and then agglomerated with a three roll or the like It is desirable to use the mixture after kneading to make it completely disappear.

[(G) Other ingredients]
In addition to the above components, the following components may be optionally added to and blended with the sealant composition for liquid crystal display cells of the present invention as required.

[Curing accelerator]
As the curing accelerator, any conventionally known ones used for thermosetting catalysts for epoxy resins can be used. In particular, those used as curing accelerators for dicyandiamide and hydrazide compounds as curing agents are preferred.

  Specific examples of the curing accelerator component include, for example, Amicure PN-23 (trade name, manufactured by Ajinomoto Co., Inc.), Hardener EH-3293S (trade name, manufactured by ARC Corporation) as an imidazole compound, Novacure HX-3721 (trade name, manufactured by Asahi Kasei Corporation), 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct As an adduct of 2-methylimidazol isocyanuric acid adduct, aliphatic amine compound and epoxy resin, Amicure PN-H, Amicure MY-24 (trade name, manufactured by Ajinomoto Co., Inc.), Hardener H-3615S (trade name) , Manufactured by ARC, Inc.), Novacure HX-3741 (trade name, Asahi Adult Ltd.) and the like, Fujicure FXE-1000 as a urea type adduct, Fujicure FXE-1030 (trade name, Fuji Kasei Co., Ltd.). Examples of adducts of an amine compound and a diisocyanate compound include UD-34 (trade name, manufactured by Hodogaya Chemical Co., Ltd.), U-CAT3502T, U-CAT3503N (trade name, manufactured by San Apro Co., Ltd.), and the like. Among these, U-CAT SA 1, U-CAT SA 102, U-CAT SA 506, U-CAT SA are used as 1,8-diazabicyclo (5,4,0) undecene-7 salts (hereinafter referred to as DBU salts). U-CAT SA 881 is preferably used as 603, U-CAT SA 810, or 1,5-diazabicyclo (4,3,0) nonene-5 salts (hereinafter referred to as DBN salts). Or two or more of them may be used in combination.

  Among the above examples, dimethylurea compounds, DBU salts, and DBN salts are specifically preferably used because of their low activity at room temperature and excellent potential.

  As the addition amount of the curing accelerator in the sealing agent composition for liquid crystal display cells of the present invention, it is preferable to add in the range of 0.1 to 6% by mass of the whole composition. More preferably, it is added in the range of 0.5 to 3% by mass. If the amount added is too small, the thermosetting property may decrease, and conversely if too large, the preservability of the sealant composition may tend to decrease.

[Coupling agent]
Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ-methacrylic acid. Roxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminop Pyrtriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, γ-isocyanatopropyltriethoxysilane, etc. Silane coupling agents, titanium coupling agents, aluminum coupling agents, imidazole silane coupling agents, and the like. These can be used singly or in combination of two or more. Among these, it is preferable to use a silane coupling agent, and it is possible to obtain a sealant composition for a liquid crystal display cell that is excellent in moisture resistance reliability and has a small decrease in adhesive strength after moisture absorption deterioration.

  When using the said coupling agent, the usage-amount is about 0.5-2.0 mass% with respect to the said inorganic filler.

[Others]
In addition to the component (F), the liquid crystal display cell sealant composition of the present invention contains a thermoplastic resin such as silicone fine particles, silicone rubber, liquid polybutadiene rubber, and acrylic core-shell fine particles, in addition to the component (F). May be.

  Furthermore, if necessary, a polymerization inhibitor, an antifoaming agent, a leveling agent, an ion trapping agent, and other additives can be blended.

[Preparation of sealant composition for liquid crystal display cell]
The sealing agent composition for a liquid crystal display cell of the present invention can be obtained by stirring, mixing and dispersing the above-mentioned components simultaneously or separately while applying heat treatment as necessary. The apparatus used for stirring, mixing, and dispersing these mixtures is not particularly limited, and a raikai machine, a three-roll, a ball mill, a planetary mixer, and the like equipped with a stirring and heating device can be used. You may combine these apparatuses suitably.

In addition, the sealing compound composition for liquid crystal display cells obtained in this way can be hardened by ultraviolet irradiation and heating. In this case, the curing conditions can be selected from a variety is not particularly limited, illuminance 80~150mW / cm ^2, in terms of light quantity is irradiated with ultraviolet rays under conditions of 2,000~3,000mJ / cm ^2, followed by 110 to 130 It is possible to employ a method of heating at 150 ° C., particularly 115 to 125 ° C. for 30 to 120 minutes, particularly 45 to 90 minutes.

[Application of sealing composition for liquid crystal display cell]
When the sealing agent composition of the present invention is used as a sealing agent for a liquid crystal display cell, the application method is not particularly limited, and for example, it can be applied to the production of a liquid crystal panel by the following method.

In the liquid crystal display cell sealing composition of the present invention, glass fiber (short fiber having a diameter of 5 μmφ) as a spacer is blended so as to be 1% by mass, and dispersed and defoamed with a vacuum stirring defoaming device. Sort. Next, after drawing a square pattern with a line width of 0.2 mm and a height of 0.05 mm on a glass substrate using a dispenser device, liquid crystal (MLC-6628, manufactured by Merck & Co., Inc.) is placed in the dispenser device. Apply a fixed amount and spot. Next, this glass substrate is placed under reduced pressure (13.3 Pa), and another glass substrate is overlaid. Thereafter, after returning the glass substrate to atmospheric pressure, and UV irradiation (the quantity 2.5 J / cm ^2, illuminance 100 mW / cm ²⁾ temporary fixing (temporary curing). Subsequently, a test panel is produced by performing heat curing of the sealing agent and reorientation of the liquid crystal under conditions of 120 ° C. × 1 hour in a hot air dryer.
About the obtained test panel, it can be confirmed whether there is no problem by confirming the presence or absence of alignment unevenness of the sealant / liquid crystal boundary portion with a polarizing microscope.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to preparation examples, synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts and% mean mass parts and mass%, respectively, and the viscosity is a value at 25 ° C. measured by an E-type viscometer (HPDV-III, manufactured by Brookfield) according to JIS Z-8803. Indicates.

（式中、Ｇはグリシジル基を表す。ｎは１〜５の整数を表す。） [Preparation Example 1]
Separation of phenol aralkyl type liquid epoxy resin Phenol aralkyl type epoxy resin (Mitsui Chemicals, E-XLC-4L, Epoxy equivalent) 234 g / eq, softening point 44.7 ° C., FIG. 1) A solution of 500 parts in 500 parts of toluene was charged and stirred. Thereafter, 600 parts of n-hexane was dropped into the system from the dropping tube over 1 hour. After completion of dropping, the mixture was further stirred for 2 hours, allowed to stand, and separated. The precipitated components were separated by filtration, and the supernatant was collected and concentrated under reduced pressure with an evaporator to obtain 120 parts of a liquid phenol aralkyl epoxy resin (b) (recovery rate: 24%). As a result of GPC analysis (detected with eluent THF, UV254 nm), the content ratio of the component represented by n = 1 in the following formula (1) is 83.2%, and the content ratio of the component represented by n ≧ 3 Was 2.8% (FIG. 2). Moreover, the obtained epoxy resin was a pale yellow liquid, the viscosity at 25 ° C. was 18 Pa · s, and the epoxy equivalent was 223 g / eq.

(In the formula, G represents a glycidyl group. N represents an integer of 1 to 5.)

[Preparation Example 2]
Separation of phenol aralkyl type liquid epoxy resin Phenol aralkyl type epoxy resin (Mitsui Chemicals, E-XLC-4L, epoxy equivalent) while purging nitrogen gas purge to a separable flask equipped with a stirrer and a dropping tube 234 g / eq, softening point 44.7 ° C., FIG. 1) A solution of 500 parts in 500 parts of toluene was charged and stirred. Thereafter, 670 parts of n-hexane was dropped into the system from the dropping tube over 0.5 hour. After completion of dropping, the mixture was further stirred for 2 hours, allowed to stand, and separated. The precipitated components were separated by filtration, and the supernatant was collected and concentrated under reduced pressure with an evaporator to obtain 160 parts of a liquid phenol aralkyl epoxy resin (c) (recovery rate: 32%). As a result of GPC analysis (detected with eluent THF, UV254 nm), the content ratio of the component represented by n = 1 in the above formula (1) is 72.3%, and the content ratio of the component represented by n ≧ 3 Was 12.2%. Moreover, the obtained epoxy resin was a pale yellow liquid, the viscosity at 25 ° C. was 52 Pa · s, and the epoxy equivalent was 230 g / eq.

（式中、ｍは繰り返し数を表す。）
で表されるフェノールアラルキル型フェノール樹脂２６０部が得られた。ＧＰＣ分析（溶離液ＴＨＦ、ＵＶ２５４ｎｍで検出）の結果では、式（２）で表される樹脂中で、ｍ＝１で表される成分の含有割合は９１．４％、ｎ≧３で表される成分の含有割合は１．６％であった。また、得られた樹脂の融点を測定したところ、１５５〜１６０℃であった。 [Synthesis Example 1]
Synthesis of phenol aralkyl type phenolic resin A flask equipped with a stirrer, a reflux condenser, a Dean-Stark tube, and a thermometer was charged with nitrogen gas purge, and charged with 940 parts of phenol and 138 parts of p-xylene glycol and heated to 80 ° C. Thereafter, 1.9 parts of p-toluenesulfonic acid monohydrate was added and stirred and dissolved. Thereafter, the reaction system was kept at 130 to 135 ° C. and stirred for 10 hours. After completion of the reaction, 300 parts of methyl isobutyl ketone was added, washed with water until the aqueous washing solution of the oil layer became neutral, and excess phenol, solvent, etc. were distilled off under reduced pressure under heating conditions to obtain 270 parts of a phenol resin composition. Obtained. Next, 300 parts of toluene was added to the obtained resin, sufficiently heated and dissolved, and allowed to stand at room temperature for a while. When crystals were precipitated, the system was left for 12 hours while maintaining the temperature in the system at 4 ° C. The obtained crystal is filtered under reduced pressure and dried to obtain the following formula (2) as a white powdery crystal.

(In the formula, m represents the number of repetitions.)
As a result, 260 parts of a phenol aralkyl-type phenol resin represented by the formula: In the result of GPC analysis (eluent THF, detected by UV 254 nm), the content ratio of the component represented by m = 1 in the resin represented by the formula (2) is represented by 91.4% and n ≧ 3. The content ratio of the component was 1.6%. Moreover, when melting | fusing point of obtained resin was measured, it was 155-160 degreeC.

（式中、Ｇはグリシジル基を表す。ｎは１〜５の整数を表す。）
で表されるフェノールアラルキル型エポキシ樹脂（ａ）２１２部を得た。ＧＰＣ分析の結果では前記式で表される樹脂中で、ｎ＝１で表される成分の含有割合は８４．０％、ｎ≧３で表される成分の含有割合は７．１％であった。また、得られたエポキシ樹脂は淡黄色の液状であり、２５℃での粘度は２２Ｐａ・ｓ、エポキシ当量は２２０ｇ／ｅｑであった。 [Synthesis Example 2]
Synthesis of phenol aralkyl type epoxy resin 145 parts of phenol aralkyl type phenol resin obtained in Synthesis Example 1 and epichlorohydrin 830 while purging nitrogen gas purge to a flask equipped with a stirrer, dropping funnel, reflux condenser, Dean-Stark tube, thermometer Parts were charged, heated to 120 ° C., and stirred and dissolved. The mixture was further refluxed for 3 hours, dehydrated, and then the temperature and the degree of vacuum were adjusted so as to reflux at 80 to 85 ° C., and 80 parts of 50% aqueous sodium hydroxide solution was added dropwise over 60 minutes. Then, it was made to react at 80-85 degreeC for further 3 hours, and the produced | generated water was removed. Subsequently, the produced salt (sodium chloride) was filtered, and excess epichlorohydrin was distilled off under heating and reduced pressure in the oil layer, and 600 parts of methyl isobutyl ketone was added to the residue and dissolved.
This methyl isobutyl ketone solution was heated to 65 ° C., 40 parts of a 10% aqueous sodium hydroxide solution was added and reacted for 3 hours, and then washed with water until the washing solution became neutral. Further, the water layer is separated and removed, and the following formula (1)

(In the formula, G represents a glycidyl group. N represents an integer of 1 to 5.)
The phenol aralkyl type epoxy resin (a) 212 represented by these was obtained. As a result of GPC analysis, in the resin represented by the above formula, the content ratio of the component represented by n = 1 was 84.0%, and the content ratio of the component represented by n ≧ 3 was 7.1%. It was. Moreover, the obtained epoxy resin was a pale yellow liquid, the viscosity at 25 ° C. was 22 Pa · s, and the epoxy equivalent was 220 g / eq.

[Synthesis Example 3]
Synthesis of methacrylate modified compound In a flask equipped with a stirrer, a reflux condenser, and a thermometer, 172 g of bisphenol A type epoxy resin (trade name: EXA-850CRP, manufactured by Dainippon Ink and Chemicals), 69 g of methacrylic acid, tri 1 g of phenylphosphine, 0.13 g of BHT (butylhydroxytoluene) and 100 g of MIBK (methyl isobutyl ketone) were charged, and the raw materials were dissolved while stirring, and then reacted at a temperature of 100 ° C. for 6 hours. After completion of the reaction, unreacted methacrylic acid was neutralized and removed with a saturated aqueous sodium hydrogen carbonate solution, and then washed with ion-exchanged water for purification. The ionic conductivity (CM-30V, electric conductivity meter, manufactured by Toa DKK Co., Ltd.) of the aqueous solution after washing was measured and confirmed to be 0.25 mS / m. While bubbling the purified reaction solution with dry air, it was concentrated at 70 ° C. under azeotropic dehydration and reduced pressure to completely remove and purify toluene to obtain a methacrylate-modified compound (a). As a result of GPC analysis, the reaction product obtained here was a mixture of 20% partially methacrylate-modified epoxy compound and 80% completely methacrylate-modified methacrylate compound.

[Synthesis Example 4]
Synthesis of methacrylate modified compound Into a 1 L round bottom flask equipped with a stirrer, a cooling tube and a thermometer, 172 g of bisphenol A type epoxy resin (trade name: EXA-850CRP, manufactured by Dainippon Ink & Chemicals, Inc.), methacrylic acid 43 .1 g, 1 g of triphenylphosphine, 0.13 g of BHT (butylhydroxytoluene) and 100 g of toluene were charged, and the raw materials were dissolved while stirring, and then reacted at a temperature of 100 ° C. for 6 hours. After completion of the reaction, unreacted methacrylic acid was neutralized and removed with a saturated aqueous sodium hydrogen carbonate solution, and then washed with ion-exchanged water for purification. The ionic conductivity (CM-30V, electrical conductivity meter, manufactured by Toa DKK Co., Ltd.) of the aqueous solution after washing was measured and confirmed to be 0.28 mS / m. While purifying the reaction solution after purification with dry air, azeotropic dehydration and concentration under reduced pressure at 70 ° C. were performed to completely remove and purify toluene, thereby obtaining a methacrylate-modified compound (b). When the weight average molecular weight (polystyrene conversion) of this resin was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, the reaction product obtained here was 20% unreacted bisphenol. It was a mixture of A-type epoxy resin, 43% partially methacrylate-modified epoxy compound, and 37% completely methacrylate-modified methacrylate compound.

[Example 1]
As the component (A), the phenol aralkyl type epoxy resin (a) obtained in Synthesis Example 2 and as the component (B), the methacrylate-modified compound (a) obtained in Synthesis Example 3 and the potential as the component (C) Hydrazide compound as a curing agent: Amicure VDH (trade name, manufactured by Ajinomoto Co., Inc.) bead mill pulverized, (D) IRGACURE 2959 (trade name: manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator (E) As an inorganic filler, fused spherical silica and other silane coupling agents: KBM-403 (trade name, γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), Table 1 Are blended in the blending amount (parts by mass) shown in Fig. 1 and kneaded uniformly with a planetary mixer, and then until the particle size of the solid raw material becomes 3 µm or less with three rolls. Thoroughly mixed and dispersed, by treating the vacuum degassing the resulting mixture to obtain a liquid crystal display cell sealant composition.

[Example 2]
A composition was obtained in the same manner as in Example 1, except that 10 parts of Zefiac F351 (trade name, manufactured by ZEON KASEI Co., Ltd.) was added as the pseudo-curable rubbery polymer fine particle of component (F).

[Examples 3 and 4]
(A) Except having replaced the component with the phenol aralkyl type epoxy resin obtained in Preparation Example 1 or 2, each component was mix | blended with the composition and quantity (mass part) which were shown in Table 1, and it carried out similarly to Example 1. To obtain a composition.

[Comparative Example 1]
(A) It replaces with a (B) component, and the Example which mix | blended each component with the composition and quantity (mass part) which were shown in Table 1 except having used the methacrylate modification epoxy compound obtained by the synthesis example 4. A composition was obtained in the same manner as in 1.

[Comparative Example 2]
A composition was obtained in the same manner as in Comparative Example 1 except that 10 parts of Zefiac F351 (trade name, manufactured by ZEON KASEI Co., Ltd.) was added as the pseudo-curable rubbery polymer fine particle of component (F).

で表される４−ｔ−ブチルカテコールとエピクロルヒドリンとの重縮合物であり、分子内にアルコール性二級水酸基とエポキシ基を２個以上含有するエポキシ樹脂：ＨＰ−８２０（商品名、大日本インキ化学工業（株）製）を用いた以外は、各成分を表１に示した組成及び量（質量部）で配合して実施例１と同様にして組成物を得た。 [Comparative Example 3]
(A) Instead of component, the following formula

HP-820 (trade name, Dainippon Ink Co., Ltd.) is a polycondensate of 4-t-butylcatechol and epichlorohydrin represented by the formula (2) and containing two or more alcoholic secondary hydroxyl groups and epoxy groups in the molecule. Except for using Chemical Industries, Ltd.), each component was blended in the composition and amount (parts by mass) shown in Table 1 to obtain a composition in the same manner as in Example 1.

[Evaluation method]
About each sealing compound composition for liquid crystal display cells obtained above, the following various tests were done, various characteristics were evaluated, and the result was shown in Table 2. The curing conditions for each composition were first photopolymerization curing by UV irradiation (UV irradiation light amount: 2.5 J / cm ² , UV illuminance: 100 mW / cm ² ), and then heat curing (120 ° C. × 1 hour). It was.

(A) Viscosity (composition)
About each composition, according to JIS Z-8803, measurement temperature: 25 ° C., shear rate: 2.00 (sec ⁻¹ ), and after 2 minutes using an E-type viscometer (HBDV-III, manufactured by Brookfield) The value of was measured.

(B) Pot life (composition)
Each composition stored hermetically in a brown polyethylene container was taken out of the freezer (−20 ° C.) and thawed over 3 hours to make the composition temperature 25 ° C. At that time, the pot life (potential life) was evaluated as follows based on the rate of change in viscosity after standing for 48 hours at 25 ° C. and an E-type viscosity value of 100.
○: Change rate with respect to initial viscosity is less than 20%, pot life is good and sufficient Δ: Change rate with respect to initial viscosity is 20 to 40%, and there is some problem in pot life ×: Change with respect to initial viscosity The rate is over 40% and the pot life is short and insufficient

(C) Preparation of liquid crystal treated sample In a 20 ml transparent vial, 1.0 g of each composition described above was added, and then 2.0 g of liquid crystal (MLC-6628, manufactured by Merck & Co., Inc.) was added. Next, the following treatment was performed to prepare a sample solution. In addition, what performed the same process without putting the said composition simultaneously was made into the blank.
The vial was placed in a 120 ° C. hot air circulating thermostat for 1 hour, and then the treated liquid crystal returned to room temperature was transferred to the sample bottle. The sealing agent constituent eluted in this liquid crystal was quantified by gas chromatography using n-tetradecane as an internal standard substance.

(D) Orientation inspection (cured product)
In 100 parts of the sealant composition for liquid crystal display cells obtained in each of the above Examples and Comparative Examples, a glass fiber (short fiber having a diameter of 5 μmφ) as a spacer is blended to 1%, and the mixture is mixed with a vacuum stirring deaerator. Dispersion defoaming was performed and dispensed into a syringe.
Next, a glass substrate coated with an alignment film (SE 7492, manufactured by Nissan Chemical Industries, Ltd .: Corning, Inc .: # 1737, size 30 mm square, thickness 0.7 mm) was rubbed with a rubbing cloth, and then width 0 .3mm, 2cm square frame line was drawn, liquid crystal (MLC-6628, manufactured by Merck & Co., Inc.) was dropped in a predetermined amount, and a glass substrate of the same size was bonded under reduced pressure so that the rubbing surface had an angle of 90 degrees. . After returning to normal pressure, a part of the sealing agent is masked (shaded area) so as not to be irradiated with UV light, irradiated with UV (light quantity: 2.5 J / cm ² , illuminance: 100 mW / cm ² ), Thermal curing was performed at 120 ° C. for 1 hour. The sealing agent and the liquid crystal interface of the obtained glass substrate were magnified 50 times with a deflection microscope, and the presence or absence of alignment unevenness in the irradiated part and the shaded part was measured and evaluated as follows.
○: No alignment unevenness was observed at the interface between the sealing agent and the liquid crystal. Δ: Orientation unevenness was observed within the range of 0.2 to 0.5 mm at the interface between the sealing agent and the liquid crystal. Unevenness was observed in a range exceeding 0.5 mm

(E) Glass transition temperature (cured product)
The sealing composition for liquid crystal display cells obtained in each of the above Examples and Comparative Examples was sandwiched between polyethylene terephthalate (PET) films so as to have a thickness of 100 μm, and then irradiated with UV (light amount 2.5 J / cm ^2). , Illuminance 100 mW / cm ² ), and then heat-cured under the conditions of 120 ° C. × 1 hour. The obtained cured product was peeled from the PET film to obtain a test piece. The glass transition temperature of the obtained test piece was measured in the tensile mode of a TMA tester manufactured by ULVAC.

(F) Adhesion test (cured product)
A sealant composition for a liquid crystal display cell in which the spacer agent is dispersed is applied to the center of a clean glass substrate (Corning Inc .: # 1737, size 20 mm square, thickness 0.7 mm). A glass substrate having a size was overlapped, and a load was applied so that the thickness was 5 μm and the diameter was 3 mm. Thereafter, UV irradiation was performed (light amount 2.5 J / cm ² , illuminance 100 mW / cm ² ), and then heat curing was performed at 120 ° C. × 1 hour. A support base material was pasted on the obtained glass surface to prepare a test piece for adhesion. The obtained specimen was measured for vertical peel strength (MPa) per unit area at a pulling speed of 5 mm / min using an autograph apparatus manufactured by Shimadzu Corporation.

GPC chart E-XLC-4L (untreated), the content of n = 1 component is 25.0%. GPC chart E-XLC-4L (after reprecipitation treatment), the content of n = 1 component is 83.2%.

Claims (5)

(A) a phenol aralkyl type epoxy resin,
(B) a reaction mixture obtained by reacting (meth) acrylic acid with an epoxy resin, wherein the content of the unmodified epoxy resin is 0 to 5% by mass;
(C) a latent curing agent,
(D) a photopolymerization initiator,
(E) A sealing agent composition for liquid crystal display cells, comprising an inorganic filler as an essential component. The phenol aralkyl type epoxy resin of component (A) is represented by the following general formula (1)

(In the formula, G represents a glycidyl group. N represents an integer of 1 to 5.)
The sealant composition according to claim 1, wherein the ratio of the component represented by the formula: n ≧ 3 is 10% by mass or less.   The sealing agent composition according to claim 1 or 2, wherein the epoxy resin of component (B) is a bisphenol type epoxy resin.   The reaction mixture of component (B) is mixed in a proportion of 0 to 5% by mass of unreacted epoxy resin, 0 to 30% by mass of partially (meth) acrylate-modified epoxy compound, and 70 to 100% by mass of total (meth) acrylate-modified compound. The sealing agent composition for liquid crystal display cells according to any one of claims 1 to 3, wherein the sealing agent composition is for liquid crystal display cells.   5. The sealing agent composition for liquid crystal display cells according to claim 1, further comprising (F) rubber-like polymer fine particles exhibiting pseudo-curability in a temperature range of 100 ° C. or lower. .

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