JP2009086291A - Liquid crystal sealing material, method for manufacturing liquid crystal display panel using the same, and liquid crystal display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid crystal sealing material with high stability of viscosity and high curing property. <P>SOLUTION: The liquid crystal sealing material is prepared which contains: (a) a radical curable resin having two or more ethylenically unsaturated bonds in the molecule; (b) a thiol compound containing two or more primary or secondary mercapto groups in the molecule, wherein the carbon atom of the β position with respect to the primary mercapto group is a tertiary or quaternary carbon; and (c) a radical polymerization initiator. In the liquid crystal sealing material, its reactivity is suppressed to a low level and its appropriate viscosity is maintained at room temperature, and at the same time, when light or heat is imparted thereto, a radical polymerization reaction and an ene-thiol reaction simultaneously occur, and as a result the liquid crystal sealing material is cured in all parts thereof within a short period of time. Consequently only an extremely little uncured portion remains in the cured product of the liquid crystal sealing material, and a high quality liquid crystal display panel in which pollution of the liquid crystal is suppressed and of which the adhesion strength of the cured product to the substrate constituting the liquid crystal display panel is high is obtained. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid crystal sealant, a method for producing a liquid crystal display panel using the same, and a liquid crystal display panel.

  In recent years, the demand for liquid crystal display panels among flat panel displays is rapidly increasing in terms of thinness, light weight, and low power consumption. Conventionally, liquid crystal display panels have been mainly used for in-vehicle applications and small electronic devices such as mobile phones, but have gradually shifted to large LCD TV applications of 30-inch type, especially for large LCD TVs for home use. The stretch is remarkable. In response to these trends, recently, the increase in size and cost of liquid crystal display panels has been accelerated. Therefore, in the field of liquid crystal display panel manufacturing, the construction of technology capable of manufacturing large-sized and high-quality liquid crystal display panels with high productivity has been attempted by reducing the manufacturing time while expanding the equipment space and minimizing the amount of investment. It is desired.

  For manufacturing liquid crystal display panels, a liquid crystal display panel manufacturing method called a liquid crystal injection method has been adopted. In the liquid crystal injection method, two transparent substrates are bonded together via a liquid crystal sealing agent, and then liquid crystal is injected into an empty liquid crystal cell formed between the two transparent substrates, and a liquid crystal display panel is formed. It is a manufacturing method. As a liquid crystal sealant used in the liquid crystal injection method, a thermosetting liquid crystal sealant (hereinafter simply referred to as a thermosetting sealant) mainly composed of an epoxy resin has been proposed (see, for example, Patent Document 1). ).

  However, in the liquid crystal injection method, low productivity is regarded as a problem because of the long liquid crystal injection time and the necessity of high-temperature heat treatment at 120 to 150 ° C. when the liquid crystal sealant is cured. . In particular, when a large liquid crystal display panel is manufactured, there is a high possibility that it takes several tens of hours or more to inject liquid crystal into an empty liquid crystal cell, and there is a concern about an extreme decrease in productivity.

  In response to this, recently, a method of manufacturing a liquid crystal display panel called a liquid crystal dropping method has attracted attention. In the liquid crystal dropping method, which is a new method, the liquid crystal is dropped onto one of the two transparent substrates, and then the transparent substrates are bonded together under a high vacuum. Therefore, even when manufacturing a large liquid crystal display panel, it is said that the liquid crystal can be filled in a few minutes, and the manufacturing time can be shortened compared with the conventional liquid crystal injection method. It is becoming mainstream as a manufacturing method. As a liquid crystal sealing agent used for the liquid crystal dropping method, a liquid crystal sealing agent having both ultraviolet curable properties and thermosetting properties has been proposed (see, for example, Patent Documents 2 and 3).

  However, in the liquid crystal dropping method, since the liquid crystal comes into contact with the uncured liquid crystal sealing agent, the liquid crystal is contaminated when the resin component or additive of the liquid crystal sealing agent is dissolved in the liquid crystal, and the display property of the liquid crystal display panel is lowered. Have a problem. Liquid crystal contamination is more likely to occur as the resin component or additive of the liquid crystal sealant becomes more compatible with the liquid crystal, and the more uncured portions remain in the cured liquid crystal sealant. Further, if an uncured portion remains in the cured product of the liquid crystal sealant, not only the liquid crystal is contaminated, but also the cured product and a substrate constituting the liquid crystal display panel (sometimes simply referred to as “substrate”). There is concern about a decrease in adhesive strength. For this reason, liquid crystal sealing agents used in the liquid crystal dropping method are less likely to contaminate the liquid crystal (low liquid crystal contamination), and the curing proceeds to every corner (high curability) in a short time. The characteristics are required.

So far, as a highly curable liquid crystal sealant, one kind selected from the group consisting of prepolymers or oligomers selected from only epoxy (meth) acrylates, hydroxylalkyl (meth) acrylates and alkylene glycol (meth) acrylates A photocurable liquid crystal sealing agent containing the above reactive diluent and a photo radical polymerization initiator has been proposed (see, for example, Patent Document 4). Moreover, as a resin composition for a liquid crystal display panel with low liquid crystal contamination, a polythiol compound having two or more thiol groups in the molecule, and a polyene compound having two or more carbon-carbon double bonds in the molecule; And a resin composition containing a radical photopolymerization initiator have been proposed (see, for example, Patent Document 5).
International Publication No. 2004/039885 Pamphlet JP 2001-133794 A JP 2002-214626 A Japanese Patent No. 2754004 JP-A-2005-336404

  However, the (meth) acrylate component described in Patent Document 4 has a high curing shrinkage rate associated with the radical photopolymerization reaction and a high hygroscopic property. Therefore, when a liquid crystal sealant made from such components is used in the production of a liquid crystal display panel, the adhesive strength between the cured product of the liquid crystal sealant and the substrate is lowered, or the moisture resistance reliability of the resulting liquid crystal display panel is lowered. There is a high possibility of doing. In addition, the (meth) acrylate component is rapidly polymerized in an atmosphere in which oxygen is not present. For this reason, when a liquid crystal sealant made from such components is applied to the liquid crystal dropping method, the liquid crystal sealant cures rapidly when the substrates are stacked under high vacuum, and the interval between the liquid crystal cells (cell gap) is reduced. In addition to being difficult to control appropriately, the adhesive strength between the cured liquid crystal sealant and the substrate is lowered.

  On the other hand, the resin composition described in Patent Document 5 has extremely high reactivity because a polythiol compound and a polyene compound are used in combination. Therefore, since the viscosity of the resin composition is likely to increase even in a low temperature region such as normal temperature, it is difficult to maintain an appropriate viscosity. As the viscosity of the liquid crystal sealant increases, the pot life at room temperature becomes shorter, for example, the applicability to the substrate decreases, resulting in decreased productivity during production of the liquid crystal display panel and the liquid crystal display panel. Cause quality degradation.

  Accordingly, the present invention is the first to provide a liquid crystal sealant that has a low liquid crystal contamination property, has an appropriate high curability, has a long pot life at room temperature, and maintains an appropriate viscosity. The purpose. In addition, by using the liquid crystal sealant of the present invention, while maintaining high productivity, the liquid crystal sealant is excellent in display properties by suppressing liquid crystal contamination, and the cured product of the liquid crystal sealant is bonded to the substrate. A second object is to provide a liquid crystal display panel having high strength and a method for manufacturing the same.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a radical curable resin, a thiol compound, and a radical polymerization initiator in combination, focusing on the raw material of the liquid crystal sealant. The present invention has been completed.

前記一般式（１）中の、
Ｒ_１およびＲ_２は、各々独立して水素原子または炭素数１〜１０のアルキル基を表し、その少なくとも一方はアルキル基を表し、
ｍは０または１〜２の整数を表し、ｎは０または１である。
［５］ 前記一般式（１）中の、ｍが０または１、ｎが０である［４］に記載の液晶シール剤。
［６］ 前記多官能アルコールが、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、および１，３，５−トリス（２−ヒドロキシエチル）イソシアヌル酸からなる群より選ばれる１つ以上の化合物である［４］に記載の液晶シール剤。
［７］ 前記（ａ）成分が、（メタ）アクリル基、アリル基、およびビニル基からなる群より選ばれる１種以上のエチレン性不飽和結合を有する有機基を２個以上含有するポリオルガノシルセスキオキサンである［１］〜［６］のいずれかに記載の液晶シール剤。
［８］ 前記オルガノポリシルセスキオキサンの数平均分子量が、５×１０^２〜１．５×１０^４であり、かつ、前記オルガノポリシルセスキオキサン中の（メタ）アクリル基、アリル基、およびビニル基に含まれるエチレン性不飽和基１当量あたりのポリオルガノシルセスキオキサンのグラム数が５０〜３００ｇ／ｅｑ．である［７］に記載の液晶シール剤。
［９］ 前記（ｃ）成分が、光エネルギーを吸収することによってラジカル種を発生する化合物であり、ベンゾフェノン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ベンゾイン化合物、およびベンゾインエーテル化合物からなる群より選ばれる１つ以上の化合物である［１］〜［８］いずれかに記載の液晶シール剤。
［１０］ （ｄ）分子内に１個以上のグリシジル基を有するエポキシ樹脂と、（ｅ）熱潜在性エポキシ硬化剤と、（ｆ）フィラーとをさらに含む［１］〜［９］いずれかに記載の液晶シール剤。 That is, the said subject is solved by the liquid-crystal sealing compound of this invention.
[1] (a) a radical curable resin having two or more ethylenically unsaturated bonds in the molecule, and (b) a thiol compound containing two or more primary or secondary mercapto groups in the molecule. A liquid crystal sealant comprising: a thiol compound in which the β-position carbon with respect to the primary mercapto group is tertiary carbon or quaternary carbon; and (c) a radical polymerization initiator.
[2] The liquid crystal sealant according to [1], wherein the liquid crystal sealant is a one-component type in which the components (a) to (c) are uniformly mixed.
[3] The radical curable resin containing the organic group having one or more ethylenically unsaturated bonds selected from the group consisting of (meth) acrylic group, allyl group, and vinyl group. The liquid crystal sealant according to [1] or [2].
[4] The component (b) is an ester compound obtained by reacting a mercapto group-containing carboxylic acid represented by the following general formula (1) with a polyfunctional alcohol [1] to [3]. Liquid crystal sealing agent in any one.

In the general formula (1),
R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which represents an alkyl group,
m represents 0 or an integer of 1 to 2, and n is 0 or 1.
[5] The liquid crystal sealant according to [4], wherein m is 0 or 1, and n is 0 in the general formula (1).
[6] The polyfunctional alcohol is one or more selected from the group consisting of trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and 1,3,5-tris (2-hydroxyethyl) isocyanuric acid. The liquid crystal sealant according to [4], which is a compound.
[7] Polyorganosyl in which the component (a) contains two or more organic groups having one or more ethylenically unsaturated bonds selected from the group consisting of (meth) acrylic groups, allyl groups, and vinyl groups The liquid crystal sealant according to any one of [1] to [6], which is sesquioxane.
[8] The number average molecular weight of the organopolysilsesquioxane is 5 × 10 ^{2 to} 1.5 × 10 ⁴ , and a (meth) acryl group, an allyl group in the organopolysilsesquioxane, And the number of grams of polyorganosilsesquioxane per equivalent of ethylenically unsaturated groups contained in the vinyl group is 50 to 300 g / eq. The liquid crystal sealant according to [7].
[9] The component (c) is a compound that generates radical species by absorbing light energy, and is selected from the group consisting of benzophenone compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, benzoin compounds, and benzoin ether compounds. The liquid crystal sealing agent according to any one of [1] to [8], which is one or more compounds.
[10] Any one of [1] to [9], further comprising (d) an epoxy resin having one or more glycidyl groups in the molecule, (e) a thermal latent epoxy curing agent, and (f) a filler. Liquid crystal sealing agent of description.

Moreover, the said subject is solved by the manufacturing method of the liquid crystal display panel of this invention.
[11] In a method for manufacturing a liquid crystal display panel manufactured by bonding two opposing substrates together with a liquid crystal sealant, a pixel array is formed using the liquid crystal sealant described in [1] to [10] above. A step of preparing one or more substrates having a frame-like display region formed so as to surround the region, and a step of dropping liquid crystal in the uncured display region or on the other substrate And a step of superimposing the substrate onto which the liquid crystal has been dropped and the other substrate under reduced pressure, and a step of curing the liquid crystal sealant sandwiched between the substrates. Method.
[12] A liquid crystal display panel obtained by the method for manufacturing a liquid crystal display panel according to [11].

  According to the present invention, it is possible to provide a liquid crystal sealant that has a low liquid crystal contamination property, has an appropriate high curability, has a long pot life at room temperature, and maintains an appropriate viscosity. it can. In addition, by using the liquid crystal sealant of the present invention, while maintaining high productivity, liquid crystal contamination is suppressed and display properties are high and good, and the cured product of the liquid crystal sealant and the substrate A liquid crystal display panel having high adhesive strength can be provided.

  Next, the present invention will be described in detail. In the present invention, a numerical range is defined using “to”, but “to” in the present invention includes a boundary value. For example, “10 to 100” means 10 or more and 100 or less.

  The liquid crystal sealant of the present invention comprises (a) a radical curable resin having two or more ethylenically unsaturated bonds in the molecule, and (b) two or more primary or secondary mercapto groups in the molecule. A thiol compound comprising: a thiol compound in which the β-position carbon with respect to the primary mercapto group is a tertiary carbon or a quaternary carbon; and (c) a radical polymerization initiator.

  When light or heat is applied to the liquid crystal sealant of the present invention as described above, radical polymerization reaction and addition of a thiol compound to an ethylenically unsaturated bond (ene-thiol reaction) occur simultaneously. Therefore, since this liquid crystal sealing agent exhibits high curability, the possibility that an uncured component will contaminate the liquid crystal is extremely low. In addition, since there are very few uncured portions in the cured product of the liquid crystal sealant, the possibility of lowering the adhesive strength between the cured product of the liquid crystal sealant and the substrate can be kept low.

  The component (b), which is a thiol compound, also acts as a continuous transfer agent during the radical polymerization reaction. The chain transfer agent means a compound that moves the active site of the reaction by a chain transfer reaction. The liquid crystal sealant containing such a chain transfer agent is prone to generate radicals during the curing reaction, and many radicals are generated. Therefore, even when the light shielding area where the wiring and the seal pattern overlap is relatively wide, high curing is achieved. Curing progresses efficiently to every corner. At this time, the curing of the liquid crystal sealant is not rapid but proceeds in a chain while maintaining an appropriate curing rate, so that it is not difficult to control the cell gap.

  Hereinafter, each raw material used as a raw material of this invention is demonstrated.

(A) Radical curable resin having two or more ethylenically unsaturated bonds in the molecule "Radical curable resin having two or more ethylenically unsaturated bonds in the molecule" It means a resin that has two or more ethylenically unsaturated bonds and exhibits radical curability. Such a radical curable resin having an ethylenically unsaturated bond is used together with a thiol compound and a radical polymerization initiator, which will be described later, when preparing a liquid crystal sealant, so that radical polymerization reaction and ene-- Since the thiol reaction occurs simultaneously, the curability is increased.

  From the viewpoint of realizing the high curability of the liquid crystal sealant, the component (a) of the present invention has at least one ethylenically unsaturated bond selected from the group consisting of a (meth) acryl group, an allyl group, and a vinyl group. It is preferable that it is a radical curable resin containing the organic group which has.

  Examples of the component (a) of the present invention include (meth) acrylic acid ester monomers or oligomers thereof, allyl alcohol derivatives, or vinyl compounds, but are not particularly limited, and two or more ethylenic groups in the molecule. A compound having a saturated bond can be used.

  Examples of the above (meth) acrylic acid ester monomers or oligomers thereof include diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol and polypropylene glycol; diacrylates of tris (2-hydroxyethyl) isocyanurate and / or Or dimethacrylate; diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; 2 mol of ethylene oxide or propylene oxide added to 1 mol of bisphenol A Diacrylate and / or dimethacrylate of the diol obtained above; 3 moles or more of ethylene oxide or propylene per mole of trimethylolpropane Diol or triacrylate and / or di or trimethacrylate of triol obtained by adding pyrene oxide; Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A Tris (2-hydroxyethyl) isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate or oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate or oligomer thereof; Polyacrylate and / or polymethacrylate of pentaerythritol; tris (acryloxyethyl) isocyanurate Caprolactone-modified tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (methacryloxyethyl) isocyanurate; polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate and / or polymethacrylate of caprolactone-modified dipentaerythritol; Hydroxypivalate neopentyl glycol diacrylate and / or dimethacrylate; caprolactone-modified hydroxypivalate neopentyl glycol diacrylate and / or dimethacrylate; ethylene oxide-modified phosphate acrylate and / or dimethacrylate; ethylene oxide-modified alkylated phosphate acrylate And / or dimethacrylate; neo pliers Lugol, trimethylolpropane, pentaerythritol oligoacrylate and / or oligomethacrylate are included.

  In addition to the above, examples of the (meth) acrylic acid ester monomer or oligomer of the present invention include a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, Epoxy (meth) acrylic ester of epoxy resin such as phenol methane type epoxy resin, triphenol ethane type epoxy resin, trisphenol type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin ) Acrylate. These compounds may be used alone or in combination of two or more.

  Examples of the allyl alcohol derivatives include triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, glycerol diallyl ether, triaryl ether Examples include, but are not limited to, methylolpropane diallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, and allyl ester resin. These compounds may be used alone or in combination of two or more.

  The vinyl compound may be a compound having one or more vinyl groups in the molecule. Preferred examples of the vinyl compound of the present invention include, but are not limited to, divinylbenzene. Vinyl compounds may be used alone or in combination of two or more.

  From the viewpoint of suppressing liquid crystal contamination, the component (a) of the present invention has two or more ethylenically unsaturated bonds selected from the group consisting of (meth) acrylic groups, allyl groups, and vinyl groups. Polyorganosilsesquioxane is preferred. The polyorganosilsesquioxane means a compound having a three-dimensional structure in which the main chain is composed of siloxane bonds, the basic structural unit is a T unit, and the T unit is repeatedly bonded. The T unit is a unit composed of one silicon, three oxygen atoms, and one organic group typified by a methyl group or a phenyl group.

  The polyorganosilsesquioxane has a rigid ladder-like molecular skeleton in which free rotation of siloxane bonds is restricted. Siloxane bonds generally have high bond energy and high thermal decomposition temperature. Therefore, polyorganosilsesquioxane has high heat resistance and high temperature reliability. In addition, the molecular skeleton having a rigid and ladder structure reduces the solubility in liquid crystals. In addition, since it has two or more ethylenically unsaturated bonds having high addition polymerization in the molecule, the reactivity is high and good. Therefore, when polyorganosilsesquioxane is used as a raw material for a liquid crystal sealant, a liquid crystal sealant having low solubility in liquid crystal and low liquid crystal contamination and high curability due to high reactivity is prepared. Can do.

When polyorganosilsesquioxane is used as a raw material for the liquid crystal sealant, the polyorganosilsesquioxane has a number average molecular weight of 5 × 10 ² to 5 from the viewpoint of realizing an appropriate viscosity and high curability of the liquid crystal sealant. Polyorganosyl within the range of 1.5 × 10 ⁴ and per equivalent of ethylenically unsaturated groups contained in the (meth) acrylic group, allyl group, and vinyl group in the polyorganosilsesquioxane The number of grams of sesquioxane is 50 to 300 g / eq. It is preferable that

前記一般式（２）中の、
Ｒ^１は少なくとも１つのエチレン性不飽和結合を有する炭素数１〜８の有機基を表し、
Ｒ^２は水素原子、炭素数１〜８の炭化水素基または芳香族炭化水素基を表す。 Furthermore, from the viewpoint of realizing the appropriate viscosity and high curability of the liquid crystal sealant, the polyorganosilsesquioxane of the present invention is obtained by hydrolyzing and condensing the compound represented by the following general formula (2). A condensate to be synthesized is preferable.

In the general formula (2),
R ¹ represents an organic group having 1 to 8 carbon atoms having at least one ethylenically unsaturated bond,
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group.

  The compound represented by the general formula (2) is an alkoxysilane compound having an ethylenically unsaturated bond. The condensate obtained by hydrolyzing the alkoxysilane compound has an ethylenically unsaturated bond and is a high molecular weight substance. Therefore, the condensate is highly reactive and good, but has low solubility in liquid crystals. Therefore, when the condensate is used as a raw material for the liquid crystal sealant, a liquid crystal sealant having high curability and low liquid crystal contamination can be obtained. When such a liquid crystal sealant is applied to a method for manufacturing a liquid crystal display panel, particularly a liquid crystal dropping method, liquid crystal contamination is suppressed, and there is almost no uncured portion remaining in the cured product of the liquid crystal sealant. An excellent liquid crystal display panel having high adhesive strength to the substrate and high display properties can be manufactured.

Examples of R ^{1 in} the general formula (2) include groups represented by —X—CH ₂ ═CH ₂ and —X—CH (CH ₃ ) ═CH ₂ . Examples of X include a single bond, — (CH ₂ ) _n —, — (CH ₂ ) _n —OCO— (where n is an integer of 0 to 8).

  In the case where the polyorganosilsesquioxane is used as a raw material for the liquid crystal sealant, from the viewpoint of keeping the liquid crystal contamination of the liquid crystal sealant low, preferred examples of the alkoxysilane compound include vinyltrialkoxysilane, 3-methacryloxypropyl Trialkoxysilane, 3-acryloxypropyltrialkoxysilane, allyltrialkoxysilane are included.

  Examples of the vinyl trialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, and vinyltributoxysilane. Examples of the 3-methacryloxypropyltrialkoxysilane include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 3-methacryloxypropyltributoxy. Silane is included. Examples of the 3-acryloxypropyltrialkoxysilane include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, and 3-acryloxypropyltributoxysilane. included. Examples of the allyltrialkoxysilane include allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, and allyltributoxysilane. These compounds may be used alone or in combination of two or more.

  Among these, as the vinyl trialkoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and allyltriethoxysilane are preferable from the viewpoint of easy availability. These compounds may be used alone or in combination of two or more, or may be used in combination with an alkoxysilane compound having no ethylenically unsaturated bond.

  Among the vinyltrialkoxysilanes, vinyltrimethoxysilane can be easily obtained, and the viscosity at room temperature is neither too high nor too low, and also has high UV curability and good liquid crystal sealant. It is particularly useful as a raw material.

  Examples of the polyorganosilsesquioxane of the present invention also include compounds in which an organic group having a thiol group is bonded to an ethylenically unsaturated bond exhibiting radical polymerizability. Polyorganosilsesquioxanes with thiol groups introduced in this way are useful for improving the curability of liquid crystal sealants because of their high reactivity to ene-thiol reactions in addition to low liquid crystal contamination. is there.

  The polyorganosilsesquioxane used as the component (a) of the present invention is not particularly limited, and a commercially available compound may be used. The obtained commercial product may be used as it is without modification, or may be chemically modified as necessary. Examples of such polyorganosilsesquioxanes that are commercially available include AC-SQ (manufactured by Toagosei Co., Ltd.). This AC-SQ is a polyorganosilsesquioxane in which the basic structural unit of the silicon-containing polymer is almost completely T units.

(B) A thiol compound containing two or more primary or secondary mercapto groups in the molecule, wherein the β-position carbon relative to the primary mercapto group is a tertiary carbon or a quaternary carbon. The liquid crystal sealant contains the component (a) “a thiol compound containing two or more primary or secondary mercapto groups in the molecule, and the β-position carbon relative to the primary mercapto group is tertiary carbon or A thiol compound that is a quaternary carbon (sometimes referred to as “the thiol compound of the present invention”) ”is used.

  The term “tertiary carbon” means that the β-position carbon relative to the primary mercapto group is bonded to one hydrogen, α-position carbon, and two organic groups. The term “quaternary carbon” means a state in which the β-position carbon with respect to the primary mercapto group is bonded to the α-position carbon and three organic groups. In the component (b) which is such a thiol compound, the ene-thiol reaction is moderately suppressed due to steric hindrance. Therefore, when the component (b) is used as a raw material for the liquid crystal sealant, the liquid crystal sealant has an appropriate viscosity and high storage stability.

  On the other hand, since the thiol compound in which the β-position carbon with respect to the primary mercapto group is primary carbon or secondary carbon easily undergoes an ene-thiol reaction, the viscosity of the liquid crystal sealing agent when used as a raw material for the liquid crystal sealing agent. Is not maintained properly, and there is a concern that the storage stability is lowered.

  It is preferable that at least one of the substituents is an alkyl group. The phrase “at least one of the substituents is an alkyl group” means that at least one of the substituents other than the main chain located at the α-position and / or the β-position with respect to the mercapto group is an alkyl group. Here, the main chain means the longest chain skeleton composed of atoms other than hydrogen containing a mercapto group.

  Among these, when the component (b) is used as a raw material for the liquid crystal sealant, from the viewpoint of increasing the reactivity of the liquid crystal sealant, the component (b) of the present invention is a mercapto represented by the following general formula (1). It is preferably an ester compound obtained by esterifying a group-containing carboxylic acid and a polyfunctional alcohol.

前記一般式（１）中の、
Ｒ_１およびＲ_２は、各々独立して水素原子または炭素数１〜１０のアルキル基を表し、その少なくとも一方はアルキル基を表し、
ここでＲ_１およびＲ_２がともに水素原子となることはなく、
Ｒ_１およびＲ_２がともにアルキル基の場合、Ｒ_１およびＲ_２は同じであってもよいし、または異なっていてもよい。前記一般式（１）において、ｍは０または１〜２の整数であり、ｎは０または１であることが好ましく、ｍが０または１であり、ｎが０であることが特に好ましい。

In the general formula (1),
R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which represents an alkyl group,
Here, R ₁ and R ₂ are not both hydrogen atoms,
When R ₁ and R ₂ are both alkyl groups, R ₁ and R ₂ may be the same or different. In the general formula (1), m is 0 or an integer of 1 or 2, n is preferably 0 or 1, m is 0 or 1, and n is particularly preferably 0.

In the general formula (1), the alkyl group having 1 to 10 carbon atoms represented by R ₁ and R ₂ may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group, an n-hexyl group, and an n-octyl group. Among these, a methyl group or an ethyl group is more preferable.

  The method for producing the ester compound by reacting the compound represented by the general formula (1) with the polyfunctional alcohol is not particularly limited. Examples of the mercapto group-containing carboxylic acid represented by the general formula (1) include 2-mercaptopropionic acid, 2-mercaptoisobutyric acid, and 3-mercaptoisobutyric acid. In addition, preferable examples of the polyfunctional alcohol include trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and 1,3,5-tris (2-hydroxyethyl) isocyanuric acid.

  Examples of the polyfunctional alcohol include alkylene glycols having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 2,3-butanediol, and tetramethylene glycol. And diethylene glycol, glycerin, dipropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol.

  Therefore, examples of compounds preferable as the component (b) of the present invention include pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (esterified product of pentaerythritol and 3-mercaptoisobutyric acid). 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) which is an esterified product of 2-hydroxyethyl) isocyanuric acid and 3-mercaptoisobutyric acid , 3H, 5H) -trione.

  The thiol compound corresponding to the component (b) of the present invention can be easily obtained as a commercial product. The commercially available thiol compounds are 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT) PE1, manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT) NR1 manufactured by Showa Denko KK).

  The component (b) preferably has a number average molecular weight of 500 to 2000 from the viewpoint of realizing an appropriate viscosity of the liquid crystal sealant and low liquid crystal contamination. The number average molecular weight can be easily measured by GPC analysis or the like. The component (b) having such a number average molecular weight is useful as a raw material for a liquid crystal sealant because it does not have a viscosity that is too high or too low and is not easily adapted to liquid crystals.

  On the other hand, when the component (b) having a number average molecular weight exceeding 2000 is used as a raw material for the liquid crystal sealant, the viscosity of the liquid crystal sealant increases, and the pot life can be shortened, for example, the applicability to the substrate is lowered. High nature. If the pot life is shortened, the yield of the liquid crystal display panel may decrease. On the other hand, when the component (b) having a number average molecular weight of less than 500 is used as a raw material for the liquid crystal sealant, the viscosity of the liquid crystal sealant becomes low and it becomes difficult to form a seal pattern appropriately. On the other hand, it may be familiar and may exhibit high liquid crystal contamination.

  In addition, the amount ratio of the component (b) is adjusted so that the equivalent ratio of the mercapto group in the component (b) to the ethylenically unsaturated double bond of the component (a) is 0.5 to 1.5. It is preferable. Such a component (b) exhibits high curability because an ene-thiol reaction is appropriately performed, and as a result, the display property is high and good, and the adhesive strength between the substrate and the cured product of the liquid crystal sealant It is possible to manufacture a high-quality liquid crystal display panel in which the height is maintained.

(C) Radical polymerization initiator The liquid crystal sealing agent of the present invention is characterized by containing (c) a radical polymerization initiator together with the component (a) which is a radical curable resin and the component (b) which is a thiol compound. To do. The radical polymerization initiator of the present invention means a compound that generates radical species by absorbing light or heat energy. Preferable examples of such radical polymerization initiators include known radical photopolymerization initiators and thermal radical polymerization initiators, but are not particularly limited.

  Preferred examples of the radical photopolymerization initiator of the present invention include benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, α-acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds. Compounds, acylphosphine oxide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds are included. These compounds may be used alone or in combination of two or more.

  Preferable examples of the thermal radical polymerization initiator of the present invention include organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, and acetophenone compounds. Examples of the organic peroxide include compounds classified into ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate. A known compound may be used as the oxide without any particular limitation. These compounds may be used alone or in combination of two or more.

  When the component (c) is used as a raw material for the liquid crystal sealant, the amount of the component (c) used is 0.01 to 100 parts by mass with respect to 100 parts by mass of the liquid crystal sealant from the viewpoint of increasing the ultraviolet curable property or the thermosetting property. 5 parts by mass is preferable. Thus, since the liquid crystal sealant in which the amount of the component (c) is appropriately adjusted is cured by the appropriately generated radical species, a homogeneous cured product is obtained with no uncured portion remaining in a short time. Obtainable.

  When a thermal radical polymerization initiator is used as the component (c), it is preferable that the 10-hour half-life temperature of the thermal radical polymerization initiator is appropriately adjusted. The 10-hour half-life temperature is the temperature at which the concentration of the thermal radical polymerization initiator becomes half the original when the thermal radical polymerization initiator is subjected to a thermal decomposition reaction at a constant temperature for 10 hours under an inert gas. Means. A preferred thermal radical polymerization initiator of the present invention has a 10-hour half-life temperature of preferably 40 to 80 ° C, and more preferably 50 to 70 ° C.

  The effect of adjusting the 10-hour half-life temperature of the thermal radical polymerization initiator as described above will be described. If the viscosity of the liquid crystal sealant at the time of heat curing is too low, the liquid crystal may leak to the outside of the seal formed with the liquid crystal sealant (leakage). Therefore, when using a thermal radical polymerization initiator as a raw material for a liquid crystal sealant, it is preferable to suppress a decrease in viscosity of the liquid crystal sealant during heat curing. In order to suppress such a decrease in viscosity, it is effective to accelerate the curing reaction of the liquid crystal sealant to accelerate the gelation. Here, the curing temperature of the liquid crystal sealant is generally 80 to 150 ° C. Therefore, if the 10-hour half-life temperature of the thermal radical polymerization initiator is 80 ° C. or lower, more preferably 70 ° C. or lower, the thermal radical polymerization initiator tends to generate radical species, and thus the curing of the liquid crystal sealant is accelerated. In addition, a decrease in viscosity during heat curing is suppressed.

  In addition, when the 10-hour half-life temperature of the thermal radical polymerization initiator is below 40 ° C., the curing reaction easily proceeds at room temperature, so the viscosity of the liquid crystal sealant is increased and the appropriate viscosity is maintained. It becomes difficult. In contrast, if the 10-hour half-life temperature of the thermal radical polymerization initiator is 40 ° C. or higher, preferably 50 ° C. or higher, the proper viscosity of the liquid crystal sealant at room temperature can be maintained, and the pot life is long. As a result, a high-quality liquid crystal display panel can be manufactured with high productivity.

The 10-hour half-life temperature of the present invention is determined as follows. First, when the thermal decomposition reaction is handled as a primary reaction equation, the relationship of the following equation (1) is established.

The half-life is a time when the concentration of the thermal radical polymerization initiator is halved, that is, when C _t = C _0/2 . Therefore, when the thermal radical polymerization initiator has a half-life at time t, the relationship of the following formula (2) is established.

ｋｄおよびΔＥの値は、Ｊ．Ｂｒａｎｄｒｕｐら著、「ポリマーハンドブック」（第４版）、第１巻、第ＩＩ／１頁、Ａ ｊｏｈｎ Ｗｉｌｅｙ＆Ｓｏｎｓ，Ｉｎｃ．Ｐｕｂｌｉｃａｔｉｏｎ、（１９９８年）（Ｐｏｌｙｍｅｒ ＨａｎｄＢｏｏｋ Ｆｏｕｒｔｈ ｅｄｉｔｉｏｎ ｖｏｌｕｍｅ１）に記載されており、Ａは上記の式３より求められる。 On the other hand, since the temperature dependence of the rate constant is expressed by the Arrhenius equation, the relationship of the following equation (3) is established.

The values of kd and ΔE Brandrup et al., “Polymer Handbook” (4th edition), Volume 1, page II / 1, A John Wiley & Sons, Inc. Publication, (1998) (Polymer Handbook Fourth edition volume 1), and A is obtained from Equation 3 above.

そして、この上記式（４）を用いて、ｔ＝１０時間とすると、１０時間半減期温度Ｔが求められる。 Here, when the formula (2) is substituted into the formula (3), the following formula (4) is established.

Then, using this equation (4), when t = 10 hours, a 10-hour half-life temperature T is obtained.

  In addition, the liquid crystal sealant of the present invention may further include (d) an epoxy resin having one or more glycidyl groups in the molecule, (e) a thermal latent epoxy curing agent, and (f) a filler. Below, the detail of each component is demonstrated.

(D) Epoxy resin having one or more glycidyl groups in the molecule The component (d) of the present invention is not particularly limited as long as it is an epoxy resin having one or more glycidyl groups in the molecule. Preferred examples of the (d) component that is an epoxy resin include aromatic diol epoxy resins, aromatic polyvalent glycidyl ether compounds, and novolac type polyvalent glycidyl ethers of novolac resins derived from phenol or cresol and formaldehyde. Examples include glycidyl ether compounds and glycidyl ether compounds of xylylene phenol resin.

  Examples of the aromatic diol epoxy resin include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin.

  The aromatic polyvalent glycidyl ether compound means an epoxy resin obtained by a reaction of a diol compound obtained by modifying the aromatic diol epoxy resin with ethylene glycol, propylene glycol, alkylene glycol or the like and epichlorohydrin. The novolak type polyvalent glycidyl ether compound means an epoxy resin obtained by a reaction of a polyphenol compound represented by polyalkenylphenol or a copolymer thereof with epichlorohydrin.

  Among them, examples of preferable epoxy resins as the component (d) include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenolmethane type epoxy resins, and triphenolethane types. Epoxy resins, trisphenol type epoxy resins, dicyclopentadiene type epoxy resins, and biphenyl type epoxy resins are included. These epoxy resins may be used alone or in combination.

  In addition, as the component (d) of the present invention, an epoxy resin having both a radical polymerizable functional group and a glycidyl group in the molecule by adding (meth) acrylic acid to the above epoxy resin is also preferably used. Can do. Such an epoxy resin partially (meth) acrylated in the molecule can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a known method.

  The component (d) preferably has a softening point temperature measured by a ring and ball method of 40 ° C. or higher, and more preferably has a weight average molecular weight in the range of 1000 to 10,000. Since such an epoxy resin has low solubility and diffusibility in liquid crystal, liquid crystal contamination is suppressed. The weight average molecular weight of the epoxy resin can be measured, for example, by gel permeation chromatography (GPC) analysis using polystyrene as a standard.

  In addition, industrially available epoxy resins often contain impurities that do not dissolve in the solvent during the synthesis. However, when an epoxy resin containing such impurities is used as a raw material for the liquid crystal sealant, ionic impurities cause the quality of the liquid crystal display panel to be corroded and the like. Therefore, as the component (d) used as a raw material for an electronic material such as a liquid crystal sealant, a highly purified resin is preferably used by sufficiently removing impurities by a molecular distillation method or the like.

(E) Heat-latent epoxy curing agent The heat-latent epoxy curing agent of the present invention is hardly mixed with an epoxy group at room temperature where the resin is normally stored, even if it is mixed in an epoxy resin, but gives heat. Means a curing agent exhibiting an epoxy group reaction activity. When such a heat-latent epoxy curing agent is used as a raw material for a liquid crystal sealant, a liquid crystal sealant having high heat curability and an appropriate viscosity at room temperature can be obtained.

  The heat-latent epoxy curing agent of the present invention is not particularly limited, and a known compound may be used as the heat-latent epoxy curing agent. Among them, amine-based heat-latent epoxy curing agents are preferably used. The amine heat latent epoxy curing agent means a compound having an amino group in the molecule and exhibiting the characteristics of the heat latent epoxy curing agent as described above. Such amine heat latent epoxy curing agents do not react at room temperature. Therefore, when the epoxy curing agent is used as a raw material for the liquid crystal sealant, the viscosity of the liquid crystal sealant does not increase at room temperature and an appropriate viscosity is maintained, but high curability is exhibited by heating.

  Examples of the amine heat latent epoxy curing agent include compounds composed of organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, polyaminoureas, and the like. These compounds may be used alone or in combination of two or more.

  From the viewpoint of obtaining a liquid crystal sealant having an appropriate viscosity at room temperature and a long pot life, the amine heat latent epoxy curing agent is particularly preferably a compound having a melting point or a softening point temperature of 70 ° C. or higher by the ring and ball method. . Examples of such amine heat latent epoxy curing agents include dicyandiamide epoxy curing agents, organic acid dihydrazides, and imidazole derivatives.

  Examples of the dicyandiamide epoxy curing agent 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.), 7,11-octadecadien-1, 18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), and sebacic acid dihydrazide (melting point 189 ° C.) are included. Examples of the imidazole derivative include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point: 215 to 225 ° C.), 2-phenylimidazole (melting point: 137 to 147). ° C).

  Further, in the amine-based heat latent epoxy curing agent of the present invention, a modification such as an amine adduct-based heat latent epoxy curing agent, a polyamine-based heat latent epoxy curing agent, and a polyaminourea-based heat latent epoxy curing agent. Also included are amine based heat latent epoxy curing agents.

  The amine adduct thermal latent epoxy curing agent means an addition compound obtained by reacting an amine compound having thermal latent curing property and catalytic activity with an arbitrary compound. Examples of the amine adduct heat latent epoxy curing agent include “Amicure MY-24 (softening point 120 ° C.)” and “Amicure MY-H (softening point 131 ° C.)” (above, manufactured by Ajinomoto Fine Techno Co., Ltd.). Is commercially available and can be easily obtained.

  A polyamine-based heat latent epoxy curing agent has a polymer structure that is a reaction product of an amine and an epoxy, and exhibits heat latent curability in which a catalytically active amine forms a stabilizing structure with any compound. Means a compound. Examples of the polyamine thermal latent epoxy curing agent include “ADEKA HARDNER EH4339S (softening point 120 to 130 ° C.)”, “ADEKA HARDNER EH4357S (softening point 73 to 83 ° C.)” (above, manufactured by ADEKA Corporation). It is commercially available and can be easily obtained.

  The polyaminourea-based heat latent epoxy curing agent means a compound having a urea bond obtained by reacting an amine, urea and an isocyanate compound. Examples of the polyaminourea-based heat latent epoxy curing agent are commercially available as “Omicure 94 (melting point 126 to 136 ° C.)”, “Omicure 52 (melting point 220 to 230 ° C.)” (PTI Japan Co., Ltd.). And is easily available.

  When the component (d) is used as a raw material for the liquid crystal sealant, the amount of the component (d) used is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant preferable. The liquid crystal sealant in which the amount of the heat latent epoxy curing agent used is adjusted as described above has a long pot life since the proper viscosity is maintained.

  When using a heat-latent epoxy curing agent as an electronic material such as a liquid crystal sealant, before preparing the liquid crystal sealant, the heat-latent epoxy curing agent to be used should have sufficient impurities by washing, recrystallization, etc. It is preferable to remove it to make it highly purified.

(F) Filler The filler of the present invention improves the adhesion reliability of the liquid crystal sealant by controlling the viscosity of the liquid crystal sealant, improving the strength of the cured product obtained by curing the liquid crystal sealant, or suppressing linear expansion. It refers to a filler used for such purposes.

  The component (f) is not particularly limited, and a known filler that is generally used for electronic materials may be used. Examples of fillers preferable as the component (f) of the present invention include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide. Inorganic fillers such as potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride and silicon nitride are included.

  Moreover, you may use the following organic fillers as long as the characteristic of a liquid-crystal sealing compound is not impaired. The organic filler is not particularly limited, and a known filler may be used. Examples of preferred organic fillers include polymethyl methacrylate, polystyrene, and copolymers obtained by copolymerizing monomers copolymerizable therewith, polyester fine particles, polyurethane fine particles, and rubber fine particles.

  Among these, an inorganic filler is preferable from the viewpoint of improving the linear expansion coefficient and shape retention of the liquid crystal sealant. Among the inorganic fillers, silicon dioxide and talc are more preferable because of their high UV transmittance and goodness.

  The shape of the filler is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an atypical shape. Moreover, it is preferable that the usage-amount of a filler shall be 2-40 mass parts with respect to 100 mass parts of liquid crystal sealing agents, and 5-30 mass parts is more preferable. Thus, the liquid-crystal sealing compound in which the usage-amount of the filler was adjusted maintains an appropriate viscosity, and is very easy to handle, such as high applicability to the substrate. In addition, since a cured product of such a liquid crystal sealant is difficult to absorb moisture, it is possible to obtain a liquid crystal display panel having high moisture-resistant adhesion reliability and good.

(G) Other additive The liquid-crystal sealing compound of this invention may contain the other additive as needed other than the various components as mentioned above. Examples of additives preferably used in the present invention include coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, plasticizers, antifoaming agents, and conductive particles. It is. These additives may be used alone or in combination of two or more.

  In addition, a spacer may be used during the production of the liquid crystal display panel from the viewpoint that the interval (gap) of the liquid crystal cell can be suitably controlled. When the spacer is used, the spacer may be included in the liquid crystal sealing agent, or the spacer may be coated on a substrate constituting the liquid crystal display panel in advance.

  Furthermore, the liquid crystal sealant of the present invention may contain a solvent as necessary. The solvent is preferably used for a liquid crystal sealant that can be applied to a liquid crystal dropping method described later. Examples of the solvent preferably used in the present invention include ketone solvents, ether solvents, acetate solvents, toluene, and hexane.

  The amount of the solvent used when preparing the liquid crystal sealant is preferably 20% by mass or less, and more preferably 10% by mass or less based on the total amount of the liquid crystal sealant. Thus, the liquid-crystal sealing compound in which the usage-amount of the solvent was adjusted maintains an appropriate viscosity when apply | coating with respect to a board | substrate. Further, when such a liquid crystal sealing agent is applied to the production of a liquid crystal display panel, the solvent is appropriately evaporated during the production process, and thus does not elute into the liquid crystal. However, when the amount of the solvent used exceeds 20% by mass with respect to the total amount of the liquid crystal sealant, the viscosity of the liquid crystal sealant becomes low and it becomes difficult to form a seal pattern. There is a concern that the solvent remains and the display property of the liquid crystal display panel is lowered.

  Examples of the ketone solvent include cyclohexanone. Examples of the ether solvent include diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol, and butyl carbitol. Examples of the acetate solvent include diethylene glycol diacetate and alkoxydiethylene glycol monoacetate.

  The method for preparing the liquid crystal sealant of the present invention is not particularly limited, and a known technique can be used. Examples of means for mixing each component of the liquid crystal sealant include a double-arm stirrer, a roll kneader, a twin screw extruder, a ball mill kneader, and a planetary stirrer, but are not particularly limited, and known kneading A machine may be used. The liquid crystal sealant suitably mixed by any method is filtered through a filter, vacuum-degassed after impurities are removed, sealed in glass bottles and plastic containers, and stored as necessary. Transported.

  Next, the manufacturing method of the liquid crystal display panel of this invention is demonstrated. The liquid crystal sealant of the present invention can be preferably applied to a known method for producing a liquid crystal display panel in which a curing process by light irradiation is incorporated. Among them, it is preferable to apply to a method for manufacturing a liquid crystal display panel that employs a liquid crystal dropping method described below, because a high-quality liquid crystal display panel can be manufactured with excellent productivity.

  The method for producing a liquid crystal display panel according to the liquid crystal dropping method of the present invention is a method for producing a liquid crystal display panel produced by bonding two opposing substrates through a liquid crystal sealant. A step of preparing one or more substrates having a frame-shaped display region formed so as to surround the pixel array region by the liquid crystal sealant; and (2) in the display region in an uncured state, or A step of dripping liquid crystal on one substrate, (3) a step of superimposing the substrate on which the liquid crystal has been dripped, and the other substrate under reduced pressure, and (4) sandwiched between the substrates. Curing the liquid crystal sealant.

  In the step (1), a liquid crystal sealant is applied to one of the two substrates, and a substrate on which a frame-shaped display area is arranged is prepared. This frame is preferably installed near the outer periphery of the substrate, but is not particularly limited. The method for applying the liquid crystal sealant on the substrate is not particularly limited. Examples of such application methods include screen printing and application by a dispenser. Moreover, the liquid crystal sealing agent may be applied to the surface of each substrate.

  Examples of the two substrates used in the liquid crystal display panel of the present invention include a glass substrate on which TFTs are formed in a matrix, a substrate on which color filters and a black matrix are formed. Examples of the material of the substrate include glass, polycarbonate, polyethylene terephthalate, polyethersulfone, and plastic such as PMMA. On the surface of such a substrate, a transparent electrode typified by indium oxide, an alignment film typified by polyimide or the like, and an inorganic ion shielding film or the like may be applied. Examples of the alignment film include known alignment films made of organic or inorganic components.

  In the step (2), an appropriate amount of liquid crystal is dropped in the uncured display region or on the other substrate. This liquid crystal dropping is usually performed under atmospheric pressure. At this time, it is preferable to adjust the dropping amount of the liquid crystal according to the size of the frame so that the liquid crystal fits in the frame. When the liquid crystal is dropped into the frame in this manner, the capacity of the liquid crystal does not exceed the capacity of the empty cell surrounded by the frame and the substrate after bonding. Therefore, since excessive pressure is not applied to the frame, there is little possibility that the seal forming the frame is broken.

  In the above description, the other substrate onto which the liquid crystal is dropped means a substrate different from the substrate having the display region. In the case where liquid crystal is dropped onto a substrate on which such a seal is not disposed, the liquid crystal may be dropped at an arbitrary position on the other substrate that can serve as a display region when the substrates are overlapped with each other.

  In the step (3), the substrate on which the liquid crystal has been dropped and the other substrate are superposed under reduced pressure. The overlapping of the substrates may be performed using a vacuum bonding apparatus or the like, but is not particularly limited.

  In general, in the liquid crystal dropping method, the substrates are superposed under reduced pressure. In this way, if the two substrates stacked under reduced pressure are returned to atmospheric pressure, the substrates can be bonded together efficiently in a short time due to the generated atmospheric pressure difference. Since the substrates bonded together using the pressure difference in this way have good adhesion, a high-quality liquid crystal display panel can be obtained.

  In the step (4), the liquid crystal sealant sandwiched between the substrates is cured. The liquid crystal sealant of the present invention is irradiated with at least an appropriate amount of light. As a result, in the liquid crystal sealant, the polymerization reaction between the radical curable resin, which is a curing accelerator, a predetermined thiol compound, or a radical photopolymerization initiator and an epoxy resin is suitably advanced, and the liquid crystal sealant is cured. To do. Moreover, when the thermosetting component is contained in the liquid-crystal sealing compound to be used, heat processing is suitably performed as needed.

  Curing conditions such as the type of light and the irradiation time during curing, or the temperature and time during heating may be appropriately selected according to the composition of the liquid crystal sealant used. For example, when the liquid crystal sealant is cured by light, ultraviolet rays are preferably used from the viewpoint of safety and workability, and the liquid crystal sealant may be irradiated within a range of 1000 to 18000 mJ under pressure. . Further, when the liquid crystal sealant is cured by heating, the liquid crystal sealant can be sufficiently cured by heating at a heating temperature in the range of 110 to 140 ° C. with no pressure applied and heating for 1 hour.

  Although the liquid crystal display panel made by the above-described manufacturing method using the liquid crystal sealant of the present invention can be obtained with excellent productivity in a short time, a cured product of the substrate and the liquid crystal sealant Since the adhesive strength is high and the liquid crystal contamination is also suppressed, extremely good display properties are exhibited.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples according to the present invention. However, the present invention is not limited to the embodiment shown here. “%” And “part” described in the following examples and comparative examples mean “% by mass” and “part by mass”, respectively.

  First, the raw material of the liquid crystal sealing agent used in the present examples and comparative examples will be described.

(A) Radical curable resin As the component (a) which is a radical curable resin having two or more ethylenically unsaturated bonds in the molecule, three types of compounds A1 to A3 are synthesized according to Synthesis Examples 1 to 3 below. They were synthesized, appropriately selected and used.

[Synthesis Example 1]
In a 500 ml four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube, 160 g of bisphenol F type epoxy resin (Epototo YDF-8170C manufactured by Toto Kasei Co., Ltd.), 72 g of acrylic acid, 0.2 g of triethanolamine The mixture was heated and mixed at 110 ° C., stirred while blowing dry air over it, and allowed to react for 5 hours. The obtained reaction solution was washed 12 times with ultrapure water to obtain a compound A1 which is a bisphenol F-type epoxy resin-modified dimethacrylate. As a result of FD-MS analysis of compound A1, the number average molecular weight of compound A1 was 484.

[Synthesis Example 2]
In a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet, 210 parts (1.42 mol) of vinyltrimethoxysilane, 76.3 parts (4.24 mol) of ion-exchanged water, 88% formic acid 2.10 parts (0.05 mol) and 210 parts of toluene were added and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the reaction solution exothermed and the temperature rose up to 20 ° C. The reaction solution was heated to 71 ° C. and hydrolyzed to distill off methanol, water, and toluene from the reaction solution. Thereafter, the reaction solution was further heated to 75 ° C. for 1 hour. When the temperature of the reaction solution reached 75 ° C., 210 parts of toluene was added, and 1.5 hours at 50 ° C./4.0×10 ⁴ Pa and further 2.5 hours at 50 ° C./2.7×10 ³ Pa. The pressure was reduced for a period of time, and methanol, water, formic acid, and toluene remaining in the reaction solution were distilled off to obtain a compound. The number average molecular weight of the obtained compound is 2.1 × 10 ³ , and the vinyl group equivalent is 86 g / eq. Met. To the obtained compound, 18.7 parts (0.09 mol) of trimethylolpropane diallyl ether was added and reacted to obtain Compound A2. This compound A2 is a polyorganosilsesquioxane having an ethylenically unsaturated bond. Moreover, the vinyl group equivalent of compound A2 is 84 g / eq. Met.

[Synthesis Example 3]
In the same reactor as in Synthesis Example 2, 130 parts (0.88 mol) of vinyltrimethoxysilane, 87.0 parts (0.44 mol) of phenyltrimethoxysilane, 70.8 parts (3.93 mol) of ion-exchanged water, 88% 2.17 parts (0.05 mol) of formic acid and 217 parts of toluene were added and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the reaction solution exothermed and the temperature rose up to 20 ° C. The reaction solution was heated and heated to 71 ° C., and further heated to 75 ° C. and heated for 1 hour to distill off methanol, water, and toluene generated by the hydrolysis from the reaction solution.

210 parts of toluene was added to the reaction solution at a liquid temperature of 75 ° C., and the pressure was reduced at 50 ° C./4.0×10 ⁴ Pa for 1.5 hours, and further at 50 ° C./2.7×10 ³ Pa for 2.5 hours. As a result, methanol, water, formic acid, and toluene remaining in the reaction solution were distilled off to obtain a compound. The obtained compound was polyorganosilsesquioxane, the number average molecular weight was 1.8 × 10 ³ , and the vinyl group equivalent was 158 g / eq. Met. To the obtained compound, 18.0 parts (0.08 mol) of trimethylolpropane diallyl ether was added and reacted to obtain Compound A3. This compound A3 is a vinyl group-containing polyorganodimethylsiloxane. Moreover, the vinyl group equivalent of compound A3 is 138 g / eq. Met.

(B) Thiol compound A thiol compound containing two or more primary or secondary mercapto groups in the molecule, wherein the β-position carbon relative to the primary mercapto group is a tertiary or quaternary carbon thiol compound. As the component (b), there are two types: (i) ditrimethylolpropane tetrakis (3-mercaptobutyrate), (ii) pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz PE-1 manufactured by Showa Denko KK). Were appropriately selected and used. The component (i) is a compound synthesized by the following method (Synthesis Example 4), and the component (ii) is a commercially available product.

[Synthesis Example 4]
First, 11.1 g (0.05 mol) of ditrimethylolpropane and 26.43 g of 3-mercaptobutanoic acid (0) were added to a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, a Dean-Stark apparatus and a cooling tube. .22 mol), 0.5 g of dodecylbenzenesulfonic acid and 200 g of toluene were added, heated to 150 ° C., and stirred for 3 hours for esterification reaction. The cooled reaction solution was neutralized by adding an aqueous sodium hydrogen carbonate solution. The neutralized reaction solution was washed 5 times with ion-exchanged water, and dehydrated and dried using anhydrous magnesium sulfate to distill off toluene. The dehydrated reaction solution was subjected to column separation with silica gel to obtain 28 g of Compound A4. This compound A4 is ditrimethylolpropane tetrakis (3-mercaptobutyrate). As a result of FD-MS analysis of the obtained compound A4, the number average molecular weight of the compound was 937.

(C) radical polymerization initiator (c) As a component, (i) 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), which is a photo radical polymerization initiator, a thermal radical polymerization initiator (Ii) Dimethyl 2,2′-azobis (2-methylpropionate) (V-601, Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 65 ° C.) was appropriately selected and used.

(D) Epoxy resin having one or more glycidyl groups in the molecule (d) As a component, bisphenol F-type epoxy resin-modified monomethacrylate synthesized in Synthesis Example 5 below was used.

[Synthesis Example 5]
In a 500 ml four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube, 160 g (0.5 mol) of bisphenol F type epoxy resin (Epototo YDF-8170C manufactured by Toto Kasei Co., Ltd.), 36 g of acrylic acid (0 0.5 mol) and 0.2 g of triethanolamine were added, stirred while blowing dry air, and heated at 110 ° C. for 5 hours to obtain a compound. The obtained compound was washed 12 times with ultrapure water to obtain a bisphenol F-type epoxy resin-modified monomethacrylate (compound A5). As a result of FD-MS analysis of the obtained compound A5, the number average molecular weight of the compound A5 was 398.

(E) Thermal Latent Epoxy Curing Agent (e) As component, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Techno Co., Ltd .; melting point 120 ° C.) used.

(F) Filler As the component (f), spherical silica (manufactured by Admafine A-802 Admatech Co., Ltd .; primary average particle size 0.7 μm) was used.

(G) Other additives (g) As component (g), γ-glycidoxypropyltrimethoxy (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent, was used.

(H) Thiol compound not applicable to the present invention (h) As component thiol compound not corresponding to component (b) of the present invention, pentaerythritol tetrakis (3-mercapbutyrate) (manufactured by Sakai Chemical Industry Co., Ltd.) It was used.

  In each of the examples and comparative examples, (i) viscosity stability of the liquid crystal sealant, (ii) adhesive strength of the liquid crystal sealant, and (iii) display properties of the liquid crystal display panel were measured and evaluated. The properties of the agent were evaluated. Details of each measurement are shown below.

(I) Viscosity stability of liquid crystal sealant The viscosity value at 25 ° C of the liquid crystal sealant was measured using an E-type viscometer. The liquid crystal sealant used for viscosity measurement was sealed by placing 20 g of the liquid crystal sealant in a light-shielding polyethylene container having an internal volume of 100 ml, and then storing the sealed liquid at 25 ° C. for 5 days. Then, after a predetermined period of time, the viscosity value at 25 ° C. is measured with an E-type viscometer, and the change in viscosity value after the lapse of 25 ° C./5 days when the viscosity value before sealing is 100 based on the measured value. The rate was calculated. At this time, when the rate of change was 50% or less, the viscosity stability was high and good (◯), and when the rate of change exceeded 50%, the viscosity stability was low and bad (x).

(Ii) Adhesive strength of liquid crystal sealant First, a liquid crystal sealant to which 1% by mass of a 5 μm glass fiber was added was screen-printed in a circular shape having a diameter of 1 mm on an alkali-free glass having a size of 25 mm × 45 mm × 5 mm. Next, the same glass paired with this substrate was bonded to a cross and fixed with a jig, and then irradiated with 100 mW / cm ² of ultraviolet rays using an ultraviolet irradiation device (USHIO INC.), A test piece in which the liquid crystal sealant was cured was prepared. At this time, the irradiation energy of ultraviolet rays was 2000 mJ. Further, in Example 5, Example 6 and Comparative Example 3 described later, after the liquid crystal sealant was photocured by ultraviolet irradiation by the above-described method, it was further tested by heating and curing in a circulation oven at 120 ° C. for 60 minutes. A piece was made.

  The obtained test piece was heat-treated at 120 ° C. for 60 minutes in a nitrogen atmosphere using an oven. Thereafter, the plane tensile strength of the test piece is set to a tensile rate of 2 mm / min using a tensile tester (model 210 manufactured by Intesco Corporation), and the plane tensile strength is reduced by peeling in a direction parallel to the glass bottom surface. It was measured. Here, the adhesive strength of the liquid crystal sealant was evaluated in two stages according to the magnitude of the plane tensile strength. That is, when the tensile strength was 5 MPa or more, the adhesive strength was high and good (◯), and when the tensile strength was less than 5 MPa, the adhesive strength was low and inferior (x).

(Iii) Displayability of liquid crystal display panel A liquid crystal sealant in which 1% by mass of 5 μm glass fiber is added on a 40 mm × 45 mm glass substrate (RT-DM88PIN EHC Co., Ltd.) with a transparent electrode and an alignment film is used. A 35 mm × 40 mm frame was drawn with a line width of 0.5 mm and a thickness of 50 μm. A dispenser (manufactured by Shotmaster Musashi Engineering Co., Ltd.) was used for the drawing.

  A liquid crystal material (MLC-11900-000 manufactured by Merck & Co., Inc.) corresponding to the cell volume after being bonded to the drawn substrate and the other substrate to be paired with a dispenser is precisely used. After dropping, the two substrates were superposed under a reduced pressure of 90 Pa and fixed under a load.

Thereafter, in Examples 1 to 4 and 6 and Comparative Examples 1 to 3 to be described later, an ultraviolet ray irradiation device (manufactured by Ushio Electric Co., Ltd.) was used to irradiate 100 mW / cm ² of ultraviolet rays, and a liquid crystal sealant A liquid crystal display panel was produced by curing. At this time, the irradiation energy of ultraviolet rays was set to 3000 mJ. A metal halide lamp was used as the light source, and an ultraviolet integrated photometer (UVR-T35 Topcon Co., Ltd.) having a measurement wavelength range of 340 to 390 nm and a peak sensitivity wavelength of 365 nm was used for measuring integrated light. . Further, in Example 6 and Comparative Example 3 described above, after irradiating with ultraviolet rays, a liquid crystal display panel was prepared by further heating and curing at 120 ° C. for 60 minutes using a circulation oven.

  On the other hand, in Example 5, the liquid crystal display was heated at 120 ° C. for 60 minutes after being temporarily cured at 70 ° C. for 30 minutes in a circulation oven without using the above-described ultraviolet irradiation device. A panel was produced.

  The liquid crystal display panel was driven by applying a voltage of 5 V to the completed liquid crystal display panel with a DC power supply device. At this time, whether or not the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealant functions normally from the beginning of driving was visually observed, and the display properties of the liquid crystal display panel were evaluated in two stages according to predetermined criteria. The display property of the liquid crystal display panel is good (○) when the liquid crystal display function is exhibited until the seal, and is 0.3 mm away from the vicinity of the seal toward the inside of the frame. When the display function has not been demonstrated so far, the display property is markedly bad (x).

[Example 1]
As component (a), 53 parts of bisphenol F-type epoxy resin-modified dimethacrylate of Synthesis Example 1; as component (b), 47 parts of ditrimethylolpropane tetrakis (3-mercaptobutyrate) of Synthesis Example 4; component (c) As a photo radical polymerization initiator, 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), as component (f), spherical silica (Admafine A-802 AD) as an inorganic filler 15 parts of Matex Co., Ltd. and 1 part of γ-glycidoxypropyltrimethoxysilane, which is a silane coupling agent, were added as component (g), and then premixed with a mixer. The obtained mixture was kneaded with three rolls until the solid raw material became 5 μm or less, and filtered with a filter having an opening of 10 μm (MSP-10-E10S ADVANTEC Co., Ltd.). A liquid crystal sealant was prepared by vacuum stirring and defoaming the mixture after filtration with a planetary stirrer.

[Example 2]
Component (a) was used in an amount of 61 parts by mass, and component (b) was replaced with 39 parts by mass of component (ii) pentaerythritol tetrakis (3-mercaptobutyrate) instead of component (i). Prepared liquid crystal sealants by the same method as in Example 1.

[Example 3]
As component (a), 32 parts by mass of compound A1 and 11 parts by mass of compound A2 are used in combination instead of compound A1, and as component (b), component (ii) is used instead of component (i). A liquid crystal sealant was prepared in the same manner as in Example 1 except that 57 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) was used.

[Example 4]
As component (a), 57 parts by mass of compound A3 is used instead of compound A1, and as component (b), instead of component (i), component (ii) pentaerythritol tetrakis (3-mercaptobutyrate) is used. ) Was prepared in the same manner as in Example 1 except that the content was changed to 43 parts by mass.

[Example 5]
As component (a), 57 parts by mass of compound A3 is used instead of compound A1, and as component (b), instead of component (i), component (ii) pentaerythritol tetrakis (3-mercaptobutyrate) is used. ) Was 43 parts by mass, and as component (c), the same method as in Example 1 was used except that the thermal radical polymerization initiator of (ii) was changed to 0.5 parts by mass instead of component (i). A liquid crystal sealant was prepared.

[Example 6]
As component (a), 47 parts by mass of compound A3 is used instead of compound A1, and as component (b), instead of component (i), component (ii) pentaerythritol tetrakis (3-mercaptobutyrate) is used. ) Was 33 parts by mass, and 20 parts by mass of the component (d) was newly used, and the liquid crystal sealant was prepared in the same manner as in Example 1 except that the component (e) was changed to 5 parts by mass.

[Comparative Example 1]
As component (a), 59 parts by mass of compound A3 is used instead of compound A1, and pentaerythritol tetrakis (3-mercaptopropionate) not corresponding to component (b) of the present invention is used instead of component (b). A liquid crystal sealant was prepared in the same manner as in Example 1 except that the amount was 41 parts by mass.

[Comparative Example 2]
As the component (a), instead of the compound A1, 50 parts by mass of the compound A1 and 50 parts by mass of the compound A3 are used in combination, and the liquid crystal seal is the same as in Example 1 except that the component (b) is not used. An agent was prepared.

[Comparative Example 3]
As component (a), 55 parts by mass of compound A3 is used instead of compound A1, (b) component is not used, and 45 parts by mass of (d) component is newly used, and (e) component is 10 masses. A liquid crystal sealant was prepared by the same method as in Example 1 except that the parts were changed to parts.

  The evaluation results in the above Examples and Comparative Examples are summarized in Table 1.

  As is clear from Table 1, it was confirmed that the liquid crystal sealant to which the present invention was applied had high viscosity stability and was good. In addition, it is confirmed that the liquid crystal display panel manufactured using such a liquid crystal sealant has a high adhesive strength between the substrate constituting the liquid crystal display panel and a cured product of the liquid crystal sealant, and further has a good display property. It was done.

  On the other hand, Comparative Example 1 is a form using a thiol compound that is outside the scope of the present invention, but it was confirmed that the viscosity stability of the liquid crystal sealant and the adhesive strength of the liquid crystal display panel were low. Although the comparative example 2 is a form which does not use the (b) component which is a thiol compound, the adhesive strength of the liquid crystal display panel fell. Although the comparative example 3 is a form which does not use (b) component, while the viscosity stability of the liquid-crystal sealing compound fell, the display property of the liquid crystal display panel became remarkably low. The reason why the display property of the liquid crystal display panel was lowered in Comparative Example 3 is considered to be that the curability of the liquid crystal sealant was kept low because no thiol compound was used.

  Since the liquid crystal sealant of the present invention uses a radical curable resin, a thiol compound, and a radical polymerization initiator in combination, although the proper viscosity is maintained at room temperature, the radical polymerization reaction is caused by applying light or heat. Occurs and curing proceeds. Further, since the ene-thiol reaction proceeds simultaneously with the radical polymerization reaction during the curing, the curing proceeds sufficiently to every corner even when the light-shielding area is wide. Therefore, when the liquid crystal sealant of the present invention is applied to the production of a liquid crystal display panel, liquid crystal contamination is suppressed and the adhesive strength between the cured product of the liquid crystal sealant and the substrate is high, resulting in high display quality and good high quality. The liquid crystal display panel can be manufactured.

Claims (12)

(A) a radical curable resin having two or more ethylenically unsaturated bonds in the molecule;
(B) a thiol compound containing two or more primary or secondary mercapto groups in the molecule, wherein the β-position carbon relative to the primary mercapto group is a tertiary carbon or a quaternary carbon;
(C) a radical polymerization initiator;
Liquid crystal sealant containing.   The liquid crystal sealant according to claim 1, wherein the liquid crystal sealant is a one-component type in which the components (a) to (c) are uniformly mixed.   2. The radical curable resin, wherein the component (a) is an organic group having one or more ethylenically unsaturated bonds selected from the group consisting of (meth) acrylic groups, allyl groups, and vinyl groups. Or the liquid-crystal sealing compound of 2. The component (b) is an ester compound obtained by reacting a mercapto group-containing carboxylic acid represented by the following general formula (1) with a polyfunctional alcohol. Liquid crystal sealant.

[In the general formula (1),
R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which represents an alkyl group,
m represents 0 or an integer of 1 to 2, and n is 0 or 1]   The liquid crystal sealing agent according to claim 4, wherein in the general formula (1), m is 0 or 1, and n is 0.   The polyfunctional alcohol is one or more compounds selected from the group consisting of trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and 1,3,5-tris (2-hydroxyethyl) isocyanuric acid. The liquid crystal sealing agent according to claim 4.   The polyorganosilsesquioxane in which the component (a) contains two or more organic groups having one or more ethylenically unsaturated bonds selected from the group consisting of (meth) acrylic groups, allyl groups, and vinyl groups The liquid crystal sealant according to any one of claims 1 to 6. The polyorganosilsesquioxane has a number average molecular weight of 5 × 10 ^{2 to} 1.5 × 10 ⁴ , and
The number of grams of polyorganosilsesquioxane per equivalent of ethylenically unsaturated groups contained in the (meth) acrylic group, allyl group, and vinyl group in the polyorganosilsesquioxane is 50 to 300 g / eq. The liquid crystal sealant according to claim 7.   The component (c) is a compound that generates radical species by absorbing light energy, and is one selected from the group consisting of benzophenone compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, benzoin compounds, and benzoin ether compounds. The liquid crystal sealant according to any one of claims 1 to 8, which is the above compound.   The liquid crystal seal according to any one of claims 1 to 9, further comprising (d) an epoxy resin having one or more glycidyl groups in the molecule, (e) a thermal latent epoxy curing agent, and (f) a filler. Agent. In the manufacturing method of a liquid crystal display panel manufactured by bonding two substrates facing each other through a liquid crystal sealant,
A step of preparing one or more substrates having a frame-shaped display region formed so that the pixel array region is surrounded by the liquid crystal sealant according to claim 1;
Dropping the liquid crystal in the uncured display area or on the other substrate;
A step of superimposing the substrate onto which the liquid crystal has been dropped and the other substrate under reduced pressure;
Curing the liquid crystal sealant sandwiched between the substrates;
A method for manufacturing a liquid crystal display panel comprising:   The liquid crystal display panel obtained by the manufacturing method of the liquid crystal display panel of Claim 11.