TW202248397A - Liquid crystal sealing agent, method for producing liquid crystal display panel, and liquid crystal display panel - Google Patents

Abstract

Provided is a liquid crystal sealing agent with which a cured article having a low Young's modulus is obtained, and which is configured such that, when the sealing agent is used in a liquid crystal display panel that has been cured, and the liquid crystal panel is subjected to a pressure treatment, the generation of roughness is suppressed. The liquid crystal sealing agent: provides a cured article having a Young's modulus of at least 0.5 GPa but less than 3.0 GPa at 23 DEG C; and includes a thermosetting agent (E) and a thermosetting compound (A) having an epoxy group in a molecule. The thermosetting agent (E) has a water solubility of not more than 5 g/100 g at 20 DEG C.

Description

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

The present invention relates to a liquid crystal sealing agent, a method for manufacturing a liquid crystal display panel, and a liquid crystal display panel.

Display panels such as liquid crystal and organic EL are widely used in image display panels of various electronic devices including mobile phones and personal computers. For example, a liquid crystal display panel includes two transparent substrates with electrodes on their surfaces, a frame-shaped sealant sandwiched between them, and a liquid crystal material sealed in a region surrounded by the sealants.

In order to manufacture liquid crystal display panels with strong resistance to shocks caused by dropping, etc., it is required to develop a highly flexible sealant that can absorb the stress caused by the above-mentioned shocks.

For example, the liquid crystal dropping method sealant described in Patent Document 1 contains a curable resin, a polymerization initiator, and a thermosetting agent (dihydrazide-based), and the 25°C storage elastic modulus of the cured product is less than 0.8 GPa , The 121°C storage elastic modulus of the hardened product is above 0.01GPa. According to Patent Document 1, impact resistance can be improved by setting the 25°C storage elastic modulus of the cured product to less than 0.8 GPa, and by setting the 121°C storage elastic modulus of the cured product to 0.01 GPa or more. Improve heat and humidity resistance. Specifically, in Patent Document 1, the aforementioned storage modulus of elasticity can be achieved by making the aforementioned curable resin a compound containing an epoxy group and a rubber structure.

Furthermore, the liquid crystal dropping method sealant described in Patent Document 2 contains a curable resin, a polymerization initiator, or a thermosetting agent (dihydrazide series), and the 25° C. storage modulus of elasticity of the cured product is low. 2.0GPa, the 25°C loss elastic modulus of the cured product is 0.1GPa or more and 1.0GPa or less. According to Patent Document 2, by reducing the storage elastic modulus of the cured product and setting the loss elastic modulus to a certain value or more, the hardened product can be easily deformed, and the shape can be easily restored (plastic deformation is difficult to occur). Improve the impact resistance of the hardened product, and it is not easy to peel off and deform even if the substrate is repeatedly deformed. Specifically, Patent Document 2 uses a compound having a polymerizable functional group and a rubber structure for the curable resin, or blends rubber particles into the sealant, so that both the storage elastic modulus and the loss elastic modulus can be achieved. .

Furthermore, the liquid crystal sealing agent for the liquid crystal dropping method described in Patent Document 3 contains a compound having epoxy groups and acryl groups in the molecule, and the glass transition temperature measured by the DMA method is below 90° C., and the tan δ is as high as 0.5. above. In addition, Patent Document 3 describes the use of a dihydrazine-based thermosetting agent. Therefore, the flexibility of the above-mentioned sealant of Patent Document 3 can be improved after hardening, and sufficient adhesive strength can be achieved even in flexible displays and curved displays.

Furthermore, the liquid crystal dropping method sealant described in Patent Document 4 contains: a curable resin, a polymerization initiator or a thermosetting agent, and an inorganic filler having a hydrophobic group on the surface at a ratio of 15% by mass or more. agent, and the 25°C storage elastic modulus of the cured product is below 2.0GPa. According to Patent Document 4, by setting the 25° C. storage elastic modulus of the cured product to 2.0 GPa or less, it is possible to prevent the panel from peeling off when the liquid crystal display element receives impact due to dropping or the like. Patent Document 4 describes that the curable resin is preferably a compound having a soft skeleton such as a ring-opened structure of a cyclic lactone. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2020/085081 [Patent Document 2] International Publication No. 2018/124023 [Patent Document 3] Japanese Patent Laid-Open No. 2018-022054 [Patent Document 4] International Publication No. 2018/207730

(Problem to be solved by the invention)

[Issues related to the first aspect] As described in Patent Documents 1 to 5, in order to improve the resistance to impacts caused by dropping or the like, various studies have been conducted on sealants that improve flexibility after curing (decrease Young's modulus). In recent years, liquid crystal display panels are expected to be further thinned, and in order to achieve thinning, the glass plate that is the substrate is also ground and thinned after the sealant is hardened. By improving the flexibility, the stress and friction on the components inside the liquid crystal display panel can be reduced, and further thinning of the liquid crystal display panel can be expected.

However, the inventors of the present invention have newly found that if the liquid crystal display panel with the cured sealant is subjected to the above-mentioned pressure treatment such as grinding, bright spots (roughness) will occur in the liquid crystal due to the thermosetting agent exuded from the sealant. , and there is a problem of deteriorating display characteristics.

The first aspect of this specification is completed in view of the above-mentioned problems, and its purpose is to provide a cured product that has a low Young's modulus and that can suppress the occurrence of roughness when a liquid crystal display panel with a cured liquid crystal sealant is subjected to a pressure treatment. A liquid crystal sealant, a method for manufacturing a liquid crystal display panel using the liquid crystal sealant, and a liquid crystal display panel manufactured using the liquid crystal sealant. (technical means to solve the problem)

The liquid crystal sealing agent of one aspect of the present invention for solving the problems related to the first aspect of the present specification contains a Young's modulus of 0.5 GPa or more and less than 3.0 GPa as measured at 23° C. A thermosetting compound (A) having an epoxy group, and a thermosetting agent (E); wherein, the thermosetting agent (E) is a thermosetting agent whose solubility in water at 20° C. is 5 g/100 g or less.

The liquid crystal sealant of an aspect of the present invention that solves the problems related to the second aspect of the present specification has a cured product with a tensile rate of 30% or more measured at 23°C, and a cured product with a thickness of 0.6mm is tested at 60°C and 90Rh. The moisture permeability under the environment is less than 50 g/m ² .

A method of manufacturing a liquid crystal display panel according to another aspect of the present invention for solving the above-mentioned problems includes: among a pair of substrates respectively provided with an alignment film, coating the above-mentioned liquid crystal sealing film on the above-mentioned alignment film of one of the substrates. agent to form a seal pattern; in the unhardened state of the seal pattern, drop the liquid crystal on one of the above-mentioned substrates and in the area of the above-mentioned seal pattern, or drop on the other substrate; make one of the above-mentioned substrates a step of overlapping with the other substrate via the seal pattern; and a step of hardening the seal pattern.

A liquid crystal display panel according to another aspect of the present invention for solving the above-mentioned problems is provided with: a pair of substrates respectively provided with an alignment film, a frame-shaped sealing member arranged between the alignment films of the pair of substrates, and a filling layer. The liquid crystal layer in the space surrounded by the sealing member between the pair of substrates; wherein the sealing member is a cured product of the liquid crystal sealing agent. (compared to the effect of previous technology)

According to the present invention, it is possible to provide a liquid crystal sealant having a low Young's modulus of the cured product and suppressing roughness when a liquid crystal display panel having a cured liquid crystal sealant is subjected to pressure treatment, and a liquid crystal using the liquid crystal sealant. A method for manufacturing a display panel, ie a liquid crystal display panel manufactured using the liquid crystal sealant.

In addition, in this specification, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryl" means acryl or methacryl, and "(meth)acryl" means acryl or methacryl. "Acrylic" means acrylic or methacrylic, and "(meth)acrylic" means acrylic or methacrylic.

1. Liquid crystal sealant One embodiment of the present invention relates to a sealant for encapsulating liquid crystals in a liquid crystal display panel (hereinafter also referred to simply as "sealant").

1-1. Materials First, the material which can be used commonly with the liquid crystal sealing compound concerning each aspect of this specification is demonstrated. The liquid crystal sealant described in each aspect can be used in combination by appropriately selecting the following materials so as to satisfy the conditions of each aspect. In addition, these materials are not essential materials of the liquid crystal sealing agent described in each aspect, and the combination of various materials is also allowed under the premise of satisfying the conditions of each aspect.

1-1-1. Hardening resin 1-1-1-1. Thermosetting compound with epoxy group in the molecule (A) The liquid crystal sealing compound concerning each aspect mentioned above may contain the thermosetting compound (A) which has 2 or more epoxy groups in a molecule|numerator as curable resin. In addition, in this specification, a thermosetting compound (A) does not include some epoxy (meth)acrylate mentioned later.

The thermosetting compound (A) may be any of monomer, oligomer or polymer. The thermosetting compound (A) can further reduce the moisture permeability of the cured product, improve the display characteristics of the obtained liquid crystal panel, and improve the reliability of the liquid crystal display panel.

The weight average molecular weight of the thermosetting compound (A) is preferably from 500 to 10000, more preferably from 500 to 5000. The weight average molecular weight of the thermosetting compound (A) was measured in terms of polystyrene using gel permeation chromatography (GPC).

The thermosetting compound (A) is preferably a compound having an aromatic ring. Examples of epoxy compounds with aromatic rings include, for example, aromatic diols represented by bisphenol A, bisphenol S, bisphenol E, bisphenol F, bisphenol AD, etc., or aromatic diols of these aromatic diols. Alcohols, modified diols such as ethylene glycol, propylene glycol, alkanediol, etc., and aromatic polyvalent glycidyl ether compounds obtained by reacting with epichlorohydrin; phenolic resins derived from phenol or cresol and formaldehyde, Polyphenols represented by polyalkenylphenol or its copolymers, etc., phenolic polyvalent glycidyl ether compounds obtained by reacting with epichlorohydrin; and glycidyl ether compounds of stubble phenol resins, etc. Among them, preferred are cresol novolak epoxy compounds, phenol novolac epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, triphenol methane epoxy compounds, and triphenol ethane epoxy compounds. Oxygen compounds, triphenol-type epoxy compounds, dicyclopentadiene-type epoxy compounds, diphenyl ether-type epoxy compounds, or biphenyl-type epoxy compounds. The thermosetting resin composition (A) may contain only one type of epoxy compound, or may contain two or more types.

In addition, Patent Document 1 and Patent Document 3 use an epoxy compound having a structure (rubber structure) having an unsaturated bond or a siloxane structure in the molecule, so that the flexibility of the cured product can be improved. However, according to the new findings of the inventors of the present invention, the compound having the above-mentioned rubber structure tends to dissolve into the liquid crystal, which causes the liquid crystal to be easily stained. Therefore, it is preferable that the thermosetting compound (A) does not substantially contain unsaturated bond and siloxane structure in the molecule. Specifically, the unsaturated bond or siloxane structure content in the molecule is preferably at most 5% by mass, more preferably at most 1% by mass.

The thermosetting compound (A) may be liquid or solid. From the viewpoint of further reducing the moisture permeability of the cured product, a solid epoxy compound is preferred. The softening point of the solid epoxy compound is preferably not less than 40°C and not more than 150°C. The softening point can be measured according to the ring and ball method stipulated in JIS K7234 (1986).

1-1-1-2. Specific hardening compound (B) In the liquid crystal sealing compound related to the above aspects, the curable resin may contain a curable resin (B) having a property ratio of 4.70 or less, a Tg of 250° C. to 340° C., and a weight average molecular weight (Mw) of 1,000 or more.

The above-mentioned "property ratio" is a value indicating the flexibility of molecules, and the smaller the parameter, the more rounded it is.

[number 1]

In the formula (1), <R ₀ ² > is the root mean square of the distances between all ends of the polymer chain. L is the root-mean-square length of each constituent unit constituting the polymer chain, and n is the number of constituent units.

The curable compound (B) whose characteristic ratio is below 4.70 can obtain a stable structure by being in a more rounded state than other resins. Therefore, the specific curable compound (B) is usually in a round state, but when a stress is applied to the cured product of the sealant, a stretched state can be obtained. On the other hand, since the specific curable compound (B) has a large state change between the circular state and the stretched state, it is easy to expand and contract after being cured, so it can be judged that the flexibility and stretchability of the cured product of the liquid crystal sealing agent are improved. In addition, by using the specific hardening compound (B) to ensure flexibility and stretchability, even if other materials are used, or the specific hardening compound (B) uses a compound having a moisture-resistant structure in the molecule, it is still difficult to Damage to the softness and stretchability of the hardened material. From the above viewpoints, the property ratio of the specific curable compound (B) is preferably 4.70 or less, more preferably 4.50 or less. The upper limit of the characteristic ratio of the specific curable compound (B) is not particularly limited, but is preferably 4.30 or more from the viewpoint of making the viscosity more stable.

The above characteristic ratio can be set to a value calculated by the Bicerano method. Bicerano method, Joseph Bicerano, "Prediction of Polymer Properties", Marcel Dekker Company, New York, 2002 The resin property prediction value calculation method recorded.

The above-mentioned specific hardening compound (B) can be, for example, a resin having hydrogen bonds in the molecule, a resin having an ortho-substituted aromatic ring, a resin having a ketone group in a repeating structure, and the like.

The above-mentioned specific curable compound (B) may be any curable compound among photocurable compounds, thermosetting compounds, etc., but it prevents the liquid crystal from being dissolved into the liquid crystal during hardening of the sealant by heating. From the viewpoint of pollution, a photocurable compound is preferable. The specific curable compound (B) of the above-mentioned photocurable compound is more preferably a compound having an ethylenically unsaturated double bond in the molecule (excluding some epoxy (meth)acrylates), and is particularly preferable from the viewpoint of high reactivity. It is a compound with (meth)acryl group.

The above-mentioned specific curable compound (B) is preferably a curable compound represented by the following general formula (2).

[chemical 1]

In the general formula (2), R ₁ represents a divalent residue derived from a polyvalent epoxy compound; R ₂ represents independently a divalent structure obtained by opening the ring of a cyclic lactone; R ₃ represents independently a A linear or branched chain alkylene group with a number of 1 or more and 6 or less; R ₄ independently represents a hydrogen atom or a methyl group.

R ₁ is a divalent residue derived from a polyvalent epoxy compound. The above-mentioned polyvalent epoxy compound example system can include for example: Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol E type epoxy resin and bisphenol F type epoxy resin; Hydrogenated bisphenol type epoxy resin Resin; Novolac epoxy resin; Biphenyl epoxy resin; Stilbene epoxy resin; Hydroquinone epoxy resin; Naphthalene skeleton epoxy resin; Tetrahydroxyphenylethane epoxy resin; Triphenylene Methane type epoxy resin; Dicyclopentadienol type epoxy resin; 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl alicyclic epoxy resins such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of -1-butanol; Diglycidyl ester of hexahydrophthalic anhydride Polyglycidyl esters of polybasic acids; Sorbitan polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diol Glycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and cyclohexanedimethanol Glycidyl ether such as glycidyl ether; Diene polymer epoxy resin such as polybutadiene or polyisoprene; Tetraglycidyl diamine diphenylmethane, tetraglycidyl diamine Glycidylamine-type epoxy resins such as methylcyclohexane, diglycidylaniline, and tetraglycidyl-m-xylylenediamine; epoxy resins containing heterocycles such as triglycerides or hydantoin; wait.

From the viewpoint of further improving the adhesiveness and heat resistance of the sealant, R ₁ is preferably a divalent structure represented by the following general formula (2).

[Chem 2]

In the general formula (2), X represents a single bond, methylene, methylmethylene, dimethylmethylene, tolylmethylene, cyclohexylene, sulfonyl, ether bond, or thioether key.

Furthermore, from the viewpoint of further improving the flexibility of the cured product (reducing the Young's modulus), X in the general formula (2) is preferably a methylene group.

R ₂ is a divalent structure obtained by ring-opening a cyclic lactone. The type of the above-mentioned cyclic lactone is not particularly limited, but it is preferably a cyclic lactone with 2 to 6 carbon atoms, more preferably a cyclic lactone with 4 to 6 carbon atoms. Examples of such cyclic lactones include: α-hydantolide (2 carbons), β-propiolactone (3 carbons), γ-butyrolactone (4 carbons), δ-valerolactone (carbon number 5), and ε-caprolactone (carbon number 6), etc. In addition, R ₂ may also be substituted. Among them, R2 is preferably derived from β _- propiolactone and γ-butyrolactone from the viewpoint of further improving the flexibility of the curable compound and further improving the flexibility of the sealant (more reducing the Young's modulus). , δ-valerolactone, and ε-caprolactone, particularly preferably derived from γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

Specifically, R ₂ is a divalent structure shown in the following general formula (3).

[Chem 3]

In the general formula (3), Y is an alkylene group having 2 to 6 carbon atoms, preferably 3 to 6 carbon atoms, and more preferably 4 to 6 carbon atoms.

In addition, Y may also be substituted. Examples of substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.

In addition, R ₂ can also be repeated from the divalent structure (divalent structure represented by the general formula (3)) obtained by opening the ring of the above-mentioned cyclic lactone. The number of repetitions in this case is not particularly limited, but is preferably 1 to 6, more preferably 1 to 5.

R ₃ is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of the above-mentioned alkylene groups include ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and hexyl. Among them, from the viewpoint of further reducing the moisture permeability of the sealant, _R3 is preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, more preferably Ethyl, Propyl, Isopropyl.

In addition, Y may also be substituted. Examples of substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.

R ₄ is a hydrogen atom or a methyl group.

Generally, the curable compound represented by formula (2) is a bifunctional (meth)acrylic resin having a repeating structure containing a ketone group and an ortho-substituted benzene ring. According to the findings of the inventors of the present invention, the curable compound represented by the general formula (2) having such a structure can easily further improve the characteristic ratio. In addition, because the hardening compound represented by the general formula (2) has a relatively large molecular weight, it is not easy to dissolve in the liquid crystal, and can easily prevent the liquid crystal from being polluted due to the dissolution of the sealant in the liquid crystal.

The curable compound represented by the general formula (2) can be synthesized according to known methods. For example, fill a reaction flask with (meth)acrylic acid ester, phthalic anhydride and cyclic lactone with a hydroxyl group, input dry air in the presence of a polymerization terminator, and react them while stirring under reflux, and add them by bonding. The polyvalent epoxy compound is input with dry air and reacted while reflux stirring, whereby the hardening compound represented by the general formula (2) can be synthesized.

The weight average molecular weight (Mw) of a specific curable compound (B) is 1000 or more. The weight average molecular weight (Mw) is preferably from 1,000 to 2,000, more preferably from 1,200 to 1,800, and most preferably from 1,400 to 1,600. If the Mw of the specific curable compound (B) is more than 1000, not only the flexibility of the cured product can be further improved (the Young's modulus is further reduced), but also the stretchability of the cured product can be further improved. When the Mw of the specific curable compound (B) is 2000 or less, the moisture permeability of the sealant can be further reduced. The Mw of the specific curable compound (B) is a value measured using polystyrene as a standard using gel permeation chromatography (GPC).

Furthermore, the glass transition temperature (Tg) of the specific curable compound (B) is not less than 250°C and not more than 340°C, preferably not less than 260 and not more than 320°C, more preferably not less than 280 and not more than 310°C. When the above-mentioned glass transition temperature is 250° C. or higher, the moisture permeability can be reduced. When the said glass transition temperature is 340 degreeC or less, the hardened|cured material of a liquid crystal sealing compound can be made softer.

1-1-1-3. Other hardening compounds (C) The curable resin of the said sealing agent may contain other curable compounds (C) other than the above. This other curable compound (C) may be any curable compound among photocurable compounds, thermosetting compounds, and the like. Examples of the other curable compound (C) may include compounds having ethylenically unsaturated double bonds in their molecules (except for some epoxy (meth)acrylates).

The other curable compound (C) may be any of monomer, oligomer or polymer. Examples of the other hardening compound (C) include compounds having a (meth)acryloyl group in the molecule. In this compound having a (meth)acryl group, the number of (meth)acryl groups per molecule may be one, or two or more.

Examples of hardening compounds containing one (meth)acryl group in one molecule include: methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyl (meth)acrylate Alkyl (meth)acrylate such as ethyl ester.

Examples of hardening compounds having two or more (meth)acryl groups in one molecule may include, for example: di(meth)acrylates derived from polyethylene glycol, propylene glycol, and polypropylene glycol; derived from Di(meth)acrylates of tris(2-hydroxyethyl)isocyanurate; obtained by adding more than 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol Di(meth)acrylates of alcohols; di(meth)acrylates derived from diols obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A or bisphenol F; Di(or tri)(meth)acrylates derived from polyols obtained by adding 2 or 3 moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; Di(meth)acrylates derived from diols obtained by adding more than 4 moles of ethylene oxide or propylene oxide to A; and tris(2-hydroxyethyl)tri(methyl)isocyanurate Acrylates, trimethylolpropane tri(meth)acrylate or its oligomers, pentaerythritol tri(meth)acrylate or its oligomers, dipentaerythritol poly(meth)acrylates, isocyanuric Tris(acryloxyethyl), caprolactone-modified isocyanuric acid tris(acryloxyethyl), caprolactone-modified isocyanuric acid tris(methacryloxyethyl), Alkyl-modified dipentaerythritol poly(meth)acrylate, caprolactone-modified dipentaerythritol poly(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, caprolactone Ester modified hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, Ethylene oxide modified phosphoric acid (meth)acrylate, Ethylene oxide modified alkylated phosphoric acid (meth)acrylate and oligomeric (meth)acrylates of neopentyl glycol, trimethylolpropane, and pentaerythritol.

As mentioned above, a compound having a structure (rubber structure) containing an unsaturated bond or a siloxane structure in the molecule is likely to be dissolved in the liquid crystal, which is likely to cause contamination of the liquid crystal. Moreover, the above-mentioned photocurable compound having a rubber structure tends to lower the flexibility of the curing rate compared to other photocurable compounds. Therefore, it is preferable that the other curable compound (C) does not substantially have an unsaturated bond and a siloxane structure in the molecule. Specifically, the unsaturated bond or siloxane structure content in the molecule is preferably at most 5% by mass, more preferably at most 1% by mass.

1-1-1-4. Partial epoxy (meth)acrylate (D) The hardening resin of the said sealing agent may contain a part of epoxy (meth)acrylate (D). Part of the epoxy (meth)acrylate (D) can improve the adhesiveness of the cured product of the sealant to the substrate.

Part of the epoxy (meth)acrylate (D) is a compound having both epoxy and (meth)acryl groups in the molecule. Among the epoxy groups of the epoxy resin with more than two functional groups, at least one ring Partially (meth)acryloyl modified epoxy resin modified by (meth)acryloyl group. Part of the epoxy (meth)acrylate (D) can be obtained by a known method, for example, by reacting an epoxy resin with more than two functional groups and (meth)acrylic acid in the presence of an alkaline catalyst.

The epoxy resin used as the raw material of some epoxy (meth)acrylate (D) should just be an epoxy resin which has 2 or more epoxy groups in a molecule|numerator. Examples of the above-mentioned epoxy resins may include bisphenol rings such as bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol AD type, and hydrogenated bisphenol type. Oxygen resin; phenol novolac type, cresol novolac type, biphenyl novolac type, and triphenol novolac type and other novolac epoxy resins; biphenyl type epoxy resin, and naphthalene type epoxy resin, etc.

Among them, bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are preferable from the viewpoint of low crystallinity and high coating stability.

In addition, the above-mentioned epoxy resin system may have a trifunctional group, a tetrafunctional group, or an epoxy resin having a greater number of epoxy groups. However, from the viewpoint of moderately adjusting the crosslinking density so as to moderately increase the bonding strength of the cured product to the substrate, a bifunctional epoxy resin is preferred.

The molar ratio of the partial epoxy (meth)acrylate (D)-based (meth)acryloyl group to the molar number of the epoxy group is preferably 1 or more, more preferably 2 or more. By increasing the molar ratio of the (meth)acryl group, it is possible to easily suppress the contamination of the liquid crystal caused by the dissolution of the sealant into the liquid crystal.

Part of the epoxy (meth)acrylate (D) has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably 300 or more and 500 or less.

1-2. Thermosetting agent (E) The sealing agent may contain a thermosetting agent (E) for curing thermosetting components such as the thermosetting compound (A), other curable compounds (C), and partial epoxy (meth)acrylate (D).

The thermosetting agent (E) is preferably a latent thermosetting agent. The so-called latent thermosetting agent does not harden the thermosetting compound (A) and other curable compounds (C) under normal storage conditions (room temperature, visible light, etc.), but if heat is applied, Compounds that harden such compounds. The thermosetting agent (E) is preferably a curing agent capable of curing epoxy compounds (hereinafter also referred to as "epoxy curing agent").

The epoxy curing agent is from the viewpoint of improving the viscosity stability of the photothermally curable resin composition without impairing the moisture resistance of the hardened product. The melting point is preferably 50°C or higher and 250°C or lower, and the melting point is more preferably 100°C or higher. And below 200°C, especially above 150°C and below 200°C.

Examples of epoxy hardeners include: dihydrazide-based thermolatent hardeners, imidazole-based thermolatent hardeners, dicyandiamide-based thermolatent hardeners, amine adduct-based thermolatent hardeners, And polyamine-based thermal latent hardeners, etc. Among these, dihydrazide-based thermolatent hardeners, imidazole-based thermolatent hardeners, amine adduct-based thermolatent hardeners, and polyamine-based thermolatent hardeners are preferred, in order to further improve the From the point of view of display properties, more preferred are imidazole-based thermolatent hardeners, amine addition-based thermolatent hardeners, and polyamine-based thermolatent hardeners, especially amine-addition-based thermolatent hardeners, And polyamine thermal latent hardener.

Examples of dihydrazine-based thermolatent hardeners include: dihydrazine adipate (melting point 181°C), 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoylurea ( Melting point 120°C), 7,11-octadecadiene-1,18-dicarbohydrazide (melting point 160°C), dodecanedioic acid dihydrazide (melting point 190°C), and sebacic acid dihydrazide (melting point 189°C) and so on.

Examples of imidazole-based thermolatent hardeners include: 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltris(melting point: 215~225°C), And 2-phenylimidazole (melting point 137~147°C), etc.

Examples of dicyandiamide-based thermal latent hardeners include dicyandiamide (melting point: 209° C.) and the like.

The amine addition type thermal latent curing agent is a thermal latent curing agent composed of a catalytically active amine compound and an addition compound obtained by reacting with an arbitrary compound. Examples of amine addition-based thermolatent hardeners include: AMICURE PN-40 (melting point: 110°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE PN-50 (melting point: 120°C) manufactured by Ajinomoto Fine-Techno Co., Ltd. , AMICURE PN-23 manufactured by Ajinomoto Fine-Techno Co., Ltd. (melting point 100°C), AMICURE PN-31 manufactured by Ajinomoto Fine-Techno Co., Ltd. (melting point 115°C), AMICURE PN-H manufactured by Ajinomoto Fine-Techno Co., Ltd. ( melting point 115° C.), AMICURE MY-24 (melting point 120° C.) manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE MY-H (melting point 131° C.) manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The polyamine-based thermal latent hardener is a thermal latent hardener with a polymer structure obtained by the reaction of amine and epoxy, for example: ADK HARDENER EH4339S (softening point 120~130°C) manufactured by ADEKA Co., Ltd., and ADK HARDENER EH4357S (softening point: 73 to 83°C) manufactured by ADEKA Co., Ltd.

1-3. Photopolymerization initiator (F) The above-mentioned sealant may also contain ingredients for starting curing (polymerization) of specific curable compounds (B), other curable compounds (C), partial epoxy (meth)acrylate (D) and other photocurable components. Photopolymerization initiator (F).

The photopolymerization initiator (F) is a compound that can start hardening (polymerization) of these compounds, and the rest are not particularly limited. For example, the photopolymerization initiator (F) may be a radical polymerization initiator, a self-cleavage photopolymerization initiator, or a dehydrogenation inorganic photopolymerization initiator.

啉基(4-甲硫基苯基)丙烷-1-酮(BASF公司製 IRGACURE 907)等α-胺基烷基苯酮；及1-羥-環己基-苯酮(BASF公司製 IRGACURE 184)等α-羥烷基苯酮等。上述氧化醯基膦系化合物例係可舉例如：2,4,6-三甲基苯偶姻二苯基氧化膦等。上述二茂鈦系化合物例係可舉例如：雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦鹽等。上述苯乙酮系化合物例係可舉例如：二乙氧基苯乙酮、2-羥-2-甲基-1-苯基丙烷-1-酮、苄基二甲縮酮、1-(4-異丙基苯基)-2-羥-2-甲基丙烷-1-酮、4-(2-羥乙氧基)苯基-(2-羥-2-丙基)酮、1-羥環己基-苯酮、2-甲基-2-

啉基(4-甲硫基苯基)丙烷-1-酮、及2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮等。上述乙醛酸苯酯系化合物例係可舉例如：乙醛酸甲基苯酯等。上述苯偶姻醚系化合物例係可舉例如：苯偶姻、苯偶姻甲醚、及苯偶姻異丙醚等。上述肟酯系化合物例係可舉例如：1,2-辛二酮-1-[4-(苯硫基)-2-(O-苯甲醯肟)](BASF公司製 IRGACURE OXE01)、及乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(0-乙醯肟)(BASF公司製 IRGACURE OXE02)等。Examples of self-cleavage photopolymerization initiators include: alkyl phenone compounds, acyl phosphine oxide compounds, titanocene compounds, acetophenone compounds, phenyl glyoxylate compounds, benzophenone compounds, Indium ether compounds, oxime ester compounds, etc. Examples of the above-mentioned alkyl phenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651 manufactured by BASF); 2-Methyl-2-

α-aminoalkylphenones such as linyl(4-methylthiophenyl)propan-1-one (IRGACURE 907 manufactured by BASF Corporation); and 1-hydroxy-cyclohexyl-benzophenone (IRGACURE 184 manufactured by BASF Corporation) and other α-hydroxyalkyl phenones, etc. Examples of the above-mentioned acylphosphine oxide compounds include, for example, 2,4,6-trimethylbenzoindiphenylphosphine oxide and the like. Examples of the above-mentioned titanocene compounds include: bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -phenyl)titanium salt, etc. The examples of above-mentioned acetophenone compounds can be enumerated for example: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-(4 -isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxy Cyclohexyl-benzophenone, 2-methyl-2-

Linyl (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone, etc. Examples of the above-mentioned phenyl glyoxylate-based compounds include methyl phenyl glyoxylate and the like. Examples of the aforementioned benzoin ether compounds include benzoin, benzoin methyl ether, and benzoin isopropyl ether. Examples of the above-mentioned oxime ester compounds include: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)] (IRGACURE OXE01 manufactured by BASF Corporation), and Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime) (IRGACURE OXE02 manufactured by BASF Corporation) Wait.

系化合物、蒽醌系化合物、及苄基系化合物等。上述二苯基酮系化合物例係可舉例如：二苯基酮、鄰苯甲醯基苯甲酸甲基-4-苯基二苯基酮、4,4'-二氯二苯基酮、羥二苯基酮、4-苯甲醯基-4'-甲基-二苯硫醚、丙烯酸化二苯基酮、3,3',4,4'-四(過氧化第三丁基羰基)二苯基酮、及3,3'-二甲基-4-甲氧基二苯基酮等。上述氧硫𠮿

系化合物例係可舉例如：氧硫𠮿

、2-氯氧硫𠮿

、1-氯-4-丙氧基氧硫𠮿

、1-氯-4-乙氧基氧硫𠮿

(Lambson Limited公司製 Speedcure CPTX)、2-異丙基𠮿

(Lambson Limited公司製 Speedcure ITX)、4-異丙基氧硫𠮿

、2,4-二甲基氧硫𠮿

、2,4-二乙基氧硫𠮿

(Lambson Limited公司製 Speedcure DETX)、2,4-二氯氧硫𠮿

、及(2-羧甲氧基氧硫𠮿

)-(聚伸丁二醇250)二酯(IGM公司製 Omnipol TX)等。上述蒽醌系化合物例係可舉例如：2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌、2-羥蒽醌(東京化成工業股份有限公司製 2-Hydroxyanthraquinone)、2,6-二羥蒽醌(東京化成工業股份有限公司製 Anthraflavic Acid)、及2-羥甲基蒽醌(純正化學股份有限公司製 2-(Hydroxymethyl)anthraquinone)等。Examples of dehydrogenation type photopolymerization initiators include: benzophenone series compounds, oxysulfide

series compounds, anthraquinone series compounds, and benzyl series compounds, etc. Examples of the above-mentioned diphenyl ketone series compounds include: diphenyl ketone, methyl-4-phenyl diphenyl ketone o-benzoylbenzoate, 4,4'-dichloro diphenyl ketone, hydroxy Benzophenone, 4-Benzyl-4'-methyl-diphenylsulfide, Acrylated Benzophenone, 3,3',4,4'-Tetrakis(tert-butylcarbonylperoxide) Diphenyl ketone, and 3,3'-dimethyl-4-methoxydiphenyl ketone, etc. Oxygensulfur

Examples of compounds can be for example: Oxysulfur 𠮿

, 2-sulfur oxychloride

, 1-Chloro-4-propoxysulfuryl 𠮿

, 1-Chloro-4-ethoxysulfuryl 𠮿

(Speedcure CPTX manufactured by Lambson Limited), 2-isopropyl methionyl

(Speedcure ITX manufactured by Lambson Limited), 4-isopropylsulfuric acid

, 2,4-Dimethylsulfuric acid 𠮿

, 2,4-Diethylsulfuric acid 𠮿

(Speedcure DETX manufactured by Lambson Limited), 2,4-Dichlorosulfuryl 𠮿

, and (2-carboxymethoxysulfur 𠮿

)-(polybutylene glycol 250) diester (Omnipol TX manufactured by IGM Corporation), etc. The examples of above-mentioned anthraquinone compounds can be for example: 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-hydroxyanthraquinone (Tokyo Chemical Industry Co., Ltd. 2-Hydroxyanthraquinone), 2,6-dihydroxyanthraquinone (Anthraflavic Acid, Tokyo Chemical Industry Co., Ltd.), and 2-hydroxymethylanthraquinone (2-(Hydroxymethyl)anthraquinone, Chunsei Chemical Co., Ltd.) Wait.

The absorption wavelength of a photoinitiator (F) is not specifically limited, For example, it can be set as the photoinitiator which absorbs the light of wavelength 360nm or more. Among them, more preferred is a photopolymerization initiator that absorbs light in the visible light region, and particularly preferred is a photopolymerization initiator that absorbs light with a wavelength of 360 nm or more and 780 nm or less, and more preferably a photopolymerization initiator that absorbs light with a wavelength of 360 nm or more and 430 nm or less. .

系化合物、蒽醌系化合物。該等之中，較佳係肟酯系化合物。Examples of photopolymerization initiators that absorb light with a wavelength of 360 nm or more include: alkyl phenone compounds, acyl phosphine oxide compounds, titanocene compounds, oxime ester compounds, oxysulfide compounds,

series compounds, anthraquinone series compounds. Among these, oxime ester-based compounds are preferred.

The molecular weight of a photoinitiator (F) can be made into 200 or more and 5000 or less, for example. If the molecular weight of the photopolymerization initiator (F) is more than 200, the photopolymerization initiator (F) will not easily dissolve in the liquid crystal. On the other hand, when the molecular weight of a photoinitiator (F) is 5000 or less, the compatibility with various curable resins improves, and the curability of a sealing agent becomes favorable easily. The molecular weight of the photopolymerization initiator (F) is more preferably from 230 to 3000, and most preferably from 230 to 1500.

The molecular weight of the photopolymerization initiator (F) is the "relative molecular weight" of the molecular structure of the main peak detected when analyzed by a high-performance liquid chromatography analyzer (HPLC: High Performance Liquid Chromatography).

系化合物的話，則為400nm)所檢測到總波峰中，屬於強度最大的波峰(波峰高度最高的波峰)。所檢測到主波峰的峰頂所對應相對分子質量，利用液相色層分析/質量分析(LC/MS：Liquid Chromatography Mass Spectrometry)便可測定。Specifically, a photopolymerization initiator (F) was dissolved in THF (tetrahydrofuran) to prepare a sample solution, and then a high-speed liquid chromatography (HPLC) measurement was performed. Then, the area percentage (the ratio of each peak area to the total peak area) of the detected peaks was obtained to confirm the presence or absence of the main peak. The so-called "main peak" refers to the characteristic detection wavelength of each compound (such as oxygen sulfur 𠮿

In the case of a compound, it is 400nm) among the total peaks detected, it belongs to the peak with the highest intensity (the peak with the highest peak height). The relative molecular mass corresponding to the peak top of the detected main peak can be determined by liquid chromatography/mass analysis (LC/MS: Liquid Chromatography Mass Spectrometry).

1-4. Inorganic filler (G) The above sealing agent may contain an inorganic filler (G). The inorganic filler (G) not only imparts predetermined hardness and linear expansion to the cured product, but also can inhibit the penetration of water through the hardened product, and further reduce the moisture permeability of the cured product.

Examples of inorganic fillers (G) may include: calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), oxide Zinc, silicon dioxide (silica), potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride, etc. Among these, silicon dioxide and talc are preferred.

The shape of the inorganic filler (G) may be a fixed shape such as a spherical shape, a plate shape, or a needle shape, or may be a non-fixed shape. When the inorganic filler (G) is spherical, the average primary particle diameter of the inorganic filler (G) is preferably 1.5 μm or less. In addition, the specific surface area of the inorganic filler (G) is preferably not less than 0.5 m ² /g and not more than 20 m ² /g. The average primary particle diameter of the inorganic filler (F) can be measured by the laser diffraction method described in JIS Z8825 (2013). The specific surface area of the filler can be measured in accordance with the BET method described in JIS Z8830 (2013).

1-5. Others In addition to the above-mentioned components, the above-mentioned sealant may also contain: thermal free radical generators, organic microparticles, coupling agents such as silane coupling agents, ion capture agents, ion exchangers, leveling agents, pigments, dyes, sensitizers, etc. Agents, plasticizers, and defoamers, etc.

Examples of the aforementioned thermal radical polymerization initiators include organic peroxides, azo compounds, benzoins, benzoin ethers, and acetophenones.

The above-mentioned organic fine particle system can reduce the residual stress during the coating of the sealant. For example, the above-mentioned organic microparticles may have a core part: an elastic core part containing conjugated diene rubber, polysiloxane rubber, etc.; Organic microparticles composed of polymers such as acrylate, vinyl monomer and epoxy monomer.

Examples of the above-mentioned silane coupling agents include: vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ- Glycidoxypropyltriethoxysilane, etc.

In addition, the said sealant may further contain the spacer etc. for adjusting the gap of a liquid crystal display panel.

2. Description of liquid crystal sealant related to each aspect 2-1. The first aspect 2-1-1. Description of Liquid Crystal Sealant The liquid crystal sealing compound related to the first aspect of this specification has a low Young's modulus of the cured product, and can suppress roughness from occurring when a liquid crystal display panel having a cured liquid crystal sealing compound is subjected to a pressure treatment.

The above-mentioned sealant has a Young's modulus of 0.5 GPa or more and less than 3.0 GPa measured at 23°C, and contains: a thermosetting compound (A) with an epoxy group in the molecule, and a solubility in water at 20°C Thermosetting agent (E) below 5g/100g. The above-mentioned Young's modulus is preferably from 0.5 GPa to 2.0 GPa, more preferably from 0.5 GPa to 1.5 GPa, and most preferably from 0.5 GPa to 1.0 GPa. By setting it as the said range, the flexibility of the said sealing compound can be improved more, the drop resistance of a liquid crystal display panel can be improved, and moisture permeability can be reduced, so that the reliability of a liquid crystal display panel can be improved.

The said Young's modulus is specifically the Young's modulus measured by the following method.

Apply the sealant to a thickness of 100 μm on the release paper using a dripper. Then, put the coated sealant in a container for nitrogen replacement, and after nitrogen pressing for 5 minutes, irradiate with 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm) and heat at 120°C for 1 Hours to make a hardened film.

The obtained cured film was cut into thin squares (length 150mm, width 10mm), using Autograph tensile testing machine (Shimadzu Corporation, AG-X), at room temperature (23°C), according to the test speed Tensile test was performed at 10mm/min, and Young's modulus was calculated from the slope of stress and strain in the elastic region.

The sealing compound having the above-mentioned Young's modulus can be prepared by various methods. For example, epoxy resin containing polysiloxane, epoxy resin with polyethylene glycol or polypropylene glycol, epoxy resin with urethane bond, epoxy resin with rubber structure, etc., are used as thermosetting compounds (A ), by adjusting the content ratio, etc., the above-mentioned characteristics can be imparted to the sealant. Alternatively, the above properties can be imparted to the sealant by using a resin with a relatively long alkyl group or a flexible compound with an aromatic ring in the molecule.

However, as described above, when the sealant having a low Young's modulus of the cured product is subjected to pressure treatment after curing, the cured product of the sealant is less prone to cracking. Therefore, a sealant having a Young's modulus of the cured product in the above-mentioned range can be effectively used for applications such as polishing a substrate after hardening and applying pressure treatment such as thinning a liquid crystal display panel. On the other hand, in liquid crystal display panels that are subjected to pressure treatment after hardening, bright spots (roughness) appear in the liquid crystal due to the thermosetting agent seeping out from the sealant. On the other hand, the liquid crystal display panel not subjected to the pressure treatment did not show roughness.

The inventors of the present invention believe that the above-mentioned roughness occurs by the following mechanism. That is, in the manufacture of a liquid crystal display panel, an uncured sealant and liquid crystals are patterned on a substrate, and another substrate is stacked thereon, and then the sealant is hardened. In this step, after the sealant and the liquid crystal are patterned, moisture in the environment slightly enters the liquid crystal during the idle time until another substrate is superimposed. If another substrate is stacked in this state and the sealant is cured by heating, the thermosetting agent in the sealant will ooze out into the liquid crystal. It is conventionally known that in order to suppress bleeding into the hydrophobic liquid crystal, it is preferable to use a hydrophilic material as the thermosetting agent. However, if a hydrophilic thermosetting agent is used, the thermosetting agent with improved mobility will be drawn closer to the moisture in the liquid crystal when heated, resulting in bleeding into the liquid crystal. The exuded thermosetting agent concentrates in the liquid crystal due to pressure treatment, vibration during polishing, etc., and it is judged that bright spots (roughness) appear.

In the above-mentioned mechanism, it is judged that if the approach of the thermosetting agent due to moisture in the liquid crystal is suppressed, the occurrence of bright spots (roughness) can be suppressed. According to this idea, the thermosetting agent (E) of this aspect uses the hydrophobic thermosetting agent which satisfies the requirement that the solubility to 20 degreeC water is 5 g/100g or less.

The above-mentioned solubility of the thermosetting agent (E) is a value measured as follows. Put 100g of water and a predetermined amount of hardener into a 300mL beaker, mix and stir for 2 hours, and judge it to be dissolved when it is visually transparent. Then, gradually reduce the amount of the thermosetting agent (E) added to the water. When the thermosetting agent (E) is added, mixed and stirred, and visually judged, the concentration of the thermosetting agent (E) that is judged to be dissolved for the first time is set as the above-mentioned Solubility.

Furthermore, the above-mentioned liquid crystal sealing agent was measured by using a dynamic viscoelasticity measuring device (rheometer) to measure the storage elastic modulus (G') and the loss elastic modulus (G''), while the above-mentioned liquid crystal sealing agent was left at 25°C. When heating in an environment of 120°C (constant temperature), the time until G' and G'' are consistent is preferably less than 450 seconds, more preferably less than 440 seconds, and most preferably less than 430 seconds. The time point when G' and G'' are consistent is also called "gelation point", and it belongs to the time point when the overall behavior of the composition changes from liquid state (G'' preferred position) to solid state (G' preferred position). Then, if the gelation point is exceeded, G' will rise sharply, and the composition will not harden rapidly. Regarding a certain composition, the shorter the time to reach the gelation point during heating, the easier the composition is to harden at the heating temperature.

In this aspect, the shorter the time to reach the gelation point when heating at a low temperature of 120° C., the better the low-temperature curability of the liquid crystal sealing compound. As mentioned above, the hydrophobic thermosetting agent used in this aspect suppresses the occurrence of bright spots (roughness), but on the other hand, it has a high affinity with hydrophobic liquid crystal molecules during curing (heating), so Bleeding into liquid crystals is known to easily occur. In particular, when it is desired to form the liquid crystal sealant that can be cured at low temperature in order to increase the selectivity of the substrate, the liquid crystal sealant is often cured by heating at low temperature for a long time. Because of this long-time heating, it is preferable to harden the liquid crystal sealing agent in a short time even at a low temperature in order to suppress excessive exudation of the thermosetting agent.

The liquid crystal sealing compound which has short time to reach the said gelation point can be prepared by various methods. For example, by selecting the latter according to the thermosetting agent (E), using a polyfunctional epoxy resin, or adding a thermal radical generator, the time to reach the gelation point can be shortened to within the above range.

Furthermore, it is preferable that the above-mentioned sealant is a hardened product with a thickness of 0.6 mm, and the moisture permeability under the environment of 60° C. and 90% Rh is less than 50 g/m ² .

The above-mentioned moisture permeability is specifically the moisture permeability measured in accordance with the following method.

The sealant was coated on the release paper with a dripper to a thickness of 300 μm. Then, put the coated sealant in a container for nitrogen replacement and perform nitrogen pressurization for 5 minutes, then irradiate with light of 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm), and heat at 120°C for 1 Hours to make a hardened film.

Place 2 sheets of cured film in an aluminum cup filled with calcium chloride (anhydrous) as a hygroscopic agent, place an aluminum ring and tighten the screws, then measure the initial weight of the entire aluminum cup. Then, the aluminum cup was placed in a constant temperature bath set at 60° C. and 90% Rh, and after 24 hours, the aluminum cup was taken out and the weight was measured. The obtained weight value was substituted into the following formula to calculate the moisture permeability. Calculation formula: Moisture permeability = (weight after test - weight before test) × film thickness / (film area × 100)

The sealant having the above moisture permeability can be prepared by various methods. For example, by using a flexible compound having an aromatic ring in the molecule, or using a compound having a circular structure as a stable structure, the above-mentioned characteristics can be imparted to the sealing agent.

Hereinafter, an example of a sealing compound having the above-mentioned characteristics will be described more specifically. The above sealing agent preferably contains other substances such as a curable resin, a photopolymerization initiator or a thermosetting agent for curing the above curable resin, and an inorganic filler.

The above sealant has a viscosity measured with an E-type viscometer at 25°C and 2.5 rpm, preferably from 200 Pa·s to 450 Pa·s, more preferably from 300 Pa·s to 400 Pa·s. If the viscosity is within the above range, the sealant applicability by a dispenser can be made favorable.

2-1-2. Combination of materials used in the first aspect, etc. In the liquid crystal sealing agent related to the first aspect, the thermosetting agent (E) is not only a thermosetting agent having a solubility in water at 20°C of 5 g/100 g or less, but also a thermosetting agent having two or more rings in the molecule can be widely used. Oxygen based thermosetting compound (A), specific curable compound (B), other curable compound (C), partial epoxy (meth)acrylate (D), photopolymerization initiator (F), inorganic Filling material (G), and other materials. At this time, as long as the Young's modulus measured at 23° C. of the cured product is 0.5 GPa or more and less than 3.0 GPa, the type of resin may be appropriately selected.

A thermosetting compound (A) can adjust various physical properties of a liquid crystal sealing compound. For example, as mentioned above, by using polysiloxane-containing epoxy resin, epoxy resin with polyethylene glycol or polypropylene glycol, epoxy resin with urethane bond, epoxy resin with rubber structure, etc. as thermosetting The compound (A) can lower the Young's modulus of the cured product.

The content of the thermosetting compound (A) is preferably an amount of 3 parts by mass or more and 30 parts by mass or less when the total mass of the curable resin is 100 parts by mass. When the content of the thermosetting compound (A) is 3 parts by mass or more, the moisture permeability of the cured product can be further reduced, and the display characteristics of the obtained liquid crystal panel can be improved. When the above-mentioned content of the thermosetting compound (A) is 30 parts by mass or less, the flexibility of the cured product can be improved more (the Young's modulus can be lowered more sufficiently), and the drop resistance can be improved. From the above viewpoint, the content of the thermosetting compound (A) is preferably from 10 parts by mass to 30 parts by mass, more preferably from 10 parts by mass to 25 parts by mass.

A specific curable compound (B) is easy to expand and contract the hardened|cured material of liquid crystal sealing compound more. In addition to improving resistance to shocks caused by dropping the liquid crystal panel, etc., it is possible to easily suppress cracking of the hardened sealant when applying pressure treatment to the liquid crystal display panel containing the cured sealant. . In particular, when the specific curable compound (B) is a curable compound represented by the general formula (2), the effect of easily stretching the cured product is more pronounced.

The content of the specific curable compound (B) is preferably an amount of not less than 40 parts by mass and not more than 90 parts by mass when the total mass of the curable resin is 100 parts by mass. When the above content of the specific hardening compound (B) is 40 parts by mass or more, the flexibility can be more fully improved (Young's modulus can be more fully reduced), and the resistance to impact caused by dropping the liquid crystal panel can be further improved. When pressurizing a liquid crystal display panel, etc., cracking of the cured product of the sealant can be further suppressed. When the said content of a specific curable compound (B) is 90 mass parts or less, the humidity resistance of hardened|cured material can be improved more, and the display characteristic of a liquid crystal panel can be improved more. From the above viewpoint, the content of the specific curable compound (B) is preferably not less than 50 parts by mass and not more than 80 parts by mass.

Other curable compounds (C) are used, for example, to provide photocurable properties to liquid crystal sealing agents using photocurable compounds. Moreover, various physical properties of a liquid crystal sealing compound can also be adjusted according to selection of another curable compound (C).

The content of other curable compounds (C) is preferably at least 0 parts by mass and less than 50 parts by mass, more preferably at least 5 parts by mass and at least 40 parts by mass, when the total mass of the curable resin is 100 parts by mass. Quantities below parts by mass.

In addition, according to the novel findings of the inventors of the present invention, a curable compound containing one (meth)acryl group in one molecule tends to be dissolved in liquid crystals, and contamination of the liquid crystals tends to occur. Therefore, from the viewpoint of liquid crystal contamination, the content of the curable compound containing one (meth)acryl group in one molecule is preferably less than 10 parts by mass when the total mass of the curable resin is 100 parts by mass. The amount is more preferably 5 parts by mass or less, particularly preferably 1 part by mass or less, and more preferably 0.1 parts by mass or less. The lower limit of the content of the curable compound containing one (meth)acryloyl group in one molecule may be 0 parts by mass.

Part of the epoxy (meth)acrylate (D) system can improve the adhesiveness of the cured product of the sealant to the substrate.

In addition, some epoxy (meth)acrylates (D) can improve the adhesiveness of the cured product, but on the other hand, it is difficult to improve the flexibility of the cured product. Therefore, from the viewpoint of further improving the flexibility of the cured product, the less the partial epoxy (meth)acrylate (D) content is, the better. From the above viewpoint, the content of a part of the epoxy (meth)acrylate (D) is preferably less than 10 parts by mass, more preferably 5 parts by mass, when the total mass of the curable resin is 100 parts by mass. The quantity of a part or less is especially preferable to be a quantity of 1 part by mass or less, and it is more preferable to be a quantity of 0.1 part by mass or less. The lower limit of the said content of some epoxy (meth)acrylates (D) can be made into 0 mass parts.

The thermosetting agent (E) is a hydrophilic thermosetting agent whose solubility in water at 20°C is 5 g/100 g or less. By setting the solubility of the thermosetting agent (E) to 5 g/100 g or less, it is possible to suppress occurrence of bright spots (roughness) caused by moisture in the liquid crystal approaching the thermosetting agent during heat curing. From the above viewpoint, the solubility is more preferably at most 3 g/100 g, and most preferably is less than 1 g/100 g. The lower limit of the above-mentioned solubility is not particularly limited, and may be 3 g/100 g or more.

The above-mentioned hydrophilic thermosetting agent (E) is preferably an imidazole-based thermolatent curing agent, an amine adduct-based thermolatent curing agent, or a polyamine-based thermolatent curing agent. It is considered that these thermosetting agents are less likely to bleed out into the liquid crystal and can more effectively suppress the occurrence of bright spots (roughness). From the viewpoint of more effectively suppressing the occurrence of bright spots (roughening), the above-mentioned hydrophilic thermosetting agent (E) is preferably a polyamine-based thermolatent curing agent.

The above-mentioned hydrophilic thermosetting agent (E) preferably has a melting point of 50°C or more and 250°C or less, more preferably a melting point, from the viewpoint of improving the viscosity stability of the thermosetting resin composition without impairing the moisture resistance of the cured product. It is above 70°C and below 150°C, and the best is above 80°C and below 120°C.

Examples of imidazole-based thermolatent hardeners include 2-phenylimidazole (melting point 137-147°C) and the like. In addition, commercially available examples of imidazole-based thermolatent curing agents include, for example, 2P4MHZ-PW manufactured by Shikoku Chemical Industry Co., Ltd.

The amine adduct-based thermolatent curing agent is a thermolatent curing agent composed of an addition compound obtained by reacting a catalytically active amine-based compound with an arbitrary compound. Examples of amine adduct-based thermolatent hardeners include: AMICURE PN-40 (melting point 110°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE PN-50 (melting point 120°C) manufactured by Ajinomoto Fine-Techno Co., Ltd. ), AMICURE PN-23 made by Ajinomoto Fine-Techno Co., Ltd. (melting point 100°C), AMICURE PN-31 made by Ajinomoto Fine-Techno Co., Ltd. (melting point 115°C), AMICURE PN-H made by Ajinomoto Fine-Techno Co., Ltd. (melting point: 115° C.), AMICURE MY-24 (melting point: 120° C.) manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE MY-H (melting point: 131° C.) manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The polyamine-based thermal latent hardener is a thermal latent hardener with a polymer structure obtained by the reaction of amine and epoxy, for example: ADK HARDENER EH4339S (softening point 120~130°C) manufactured by ADEKA Co., Ltd., and ADK HARDENER EH4357S (softening point: 73 to 83° C.) manufactured by ADEKA Co., Ltd., etc.

The content of the hydrophilic thermosetting agent (E) is preferably 10 parts by mass to 200 parts by mass, more preferably 50 parts by mass, based on 100 parts by mass of the total mass of the thermosetting compound (A). The quantity of not less than 160 parts by mass, and the amount of not less than 70 parts by mass and not more than 120 parts by mass of the extra-premium series. When the said content of a thermosetting agent (E) is 10 mass parts or more, the curability of a thermosetting compound (A) can be improved easily. When the content of the above-mentioned hydrophilic thermosetting agent (E) is 200 parts by mass or less, it is possible to more easily suppress the occurrence of bright spots (roughness) caused by the exudation of the above-mentioned hydrophilic thermosetting agent (E) into the liquid crystal.

The photopolymerization initiator (F) can initiate curing of specific curable compounds (B), other curable compounds (C), and some photocurable components such as epoxy (meth)acrylate (D) ( polymerization).

The content of the photopolymerization initiator (F) is the content of the photocurable compound (such as the above-mentioned partial epoxy (meth)acrylate (D), specific curable compound (B), and other curable compound (C) When the total mass is 100 parts by mass, it is preferable to be more than 0.01 parts by mass and less than 10 parts by mass. If the above-mentioned content of the photopolymerization initiator (F) is more than 0.01 parts by mass, the sealing agent can be easily increased. Curability. If the above content of the photopolymerization initiator (F) is 10 parts by mass or less, the contamination of the liquid crystal due to the dissolution of the photopolymerization initiator (F) into the liquid crystal can be more easily suppressed. The content of the starter (F) is more preferably 0.1 to 5 parts by mass, particularly preferably 0.1 to 3 parts by mass, and still more preferably 0.1 to 2.5 parts by mass.

The inorganic filler (G) not only imparts predetermined hardness and linear expansion to the cured product, but also can inhibit the penetration of water through the hardened product, so as to further reduce the moisture permeability of the cured product.

The content of the inorganic filler (G) is preferably from 10 parts by mass to 60 parts by mass, more preferably from 20 parts by mass to 55 parts by mass, when the total mass of the curable resin is 100 parts by mass. The following quantity is especially preferably the quantity of 20 mass parts or more and 50 mass parts or less, More preferably, it is the quantity of 20 mass parts or more and 30 mass parts or less. The moisture permeability of the cured product can be lowered so that the above-mentioned content of the inorganic filler (G) is larger. On the other hand, if the above-mentioned content of the inorganic filler (G) is not too much, the resistance to the impact caused by dropping the liquid crystal display panel can be sufficiently ensured, and the leakage of the sealant can be suppressed, and the coating can be improved. sex. It is preferable that content of an inorganic filler (G) shall be the said range from a viewpoint of obtaining these balance.

The liquid crystal sealant of this aspect may also contain: the above-mentioned thermal free radical generator, organic microparticles, silane coupling agent and other coupling agents, ion scavenger, ion exchanger, leveling agent, pigment, dye, sensitizer, plasticizer , And defoamers, etc.

It is preferable that content of the said thermal radical polymerization initiator shall be 0.01 mass part or more and 5.0 weight part or less when the sealing agent gross mass is 100 weight part. By making the said content of a thermal radical polymerization initiator 0.01 mass part or more, the thermosetting property of a sealing compound can be improved more. By making the said content of a thermal radical polymerization initiator 5.0 mass parts or more, the dispensing stability of a sealant can be improved more.

It is preferable that content of the said organic fine particle shall be the quantity of 5 mass parts or more and 17 mass parts or less when the sealing agent gross mass is 100 weight part. If the content of the organic microparticles is more than 5 parts by mass, the bonding strength between the cured product and the substrate can be further improved. On the other hand, if the above-mentioned content of the organic fine particles is 17 parts by mass or less, the amount of other components (such as curable resin) can be sufficiently increased to further increase the strength of the cured product.

It is preferable that content of the said silane coupling agent shall be the quantity of 0.01 mass part or more and 5 mass parts or less when the sealing agent gross mass is 100 weight part. If the content of the silane coupling agent is more than 0.01 parts by mass, the bonding strength between the cured product and the substrate can be further improved.

The total amount of the above-mentioned other components is preferably an amount of not less than 0.1 parts by mass and not more than 50 parts by mass when the total mass of the sealant is 100 parts by mass. If the total amount of other components is less than 50 parts by mass, the viscosity of the sealant will not be increased excessively, so that it will not be easily damaged and the coating stability of the sealant will be improved.

2-1-3. Summary of the first form According to the said 1st aspect, for example, the following liquid crystal sealing compound can be provided.

[1] A liquid crystal sealing agent, which is a cured product with a Young's modulus of 0.5 GPa or more and less than 3.0 GPa as measured at 23°C, which contains: A thermosetting compound (A) having an epoxy group in the molecule, and Thermohardener (E); Among them, the above-mentioned thermosetting agent (E) is a thermosetting agent having a solubility in water at 20° C. of 5 g/100 g or less.

[2] The liquid crystal sealing agent according to [1], wherein the thermosetting agent (E) is selected from an imidazole-based thermolatent curing agent, an amine adduct-based thermolatent curing agent, and a polyamine-based thermolatent curing agent. Select at least one thermal curing agent from the group consisting of permanent curing agents.

[3] The liquid crystal sealing compound as described in [1] or [2], wherein the storage elastic modulus (G') and the loss elastic modulus (G'' ), while heating the liquid crystal sealing compound at 25°C at 120°C, the time until G' and G'' coincide is 450 seconds or less.

[4] The liquid crystal sealing agent according to any one of [1] to [3], which contains: a property ratio of 4.70 or less, a Tg of 250° C. to 340° C., and a weight average molecular weight (Mw) of Hardening compound (B) of 1000 or more.

(一般式(2)中，R ₁係表示源自多價環氧化合物的二價殘基；R ₂係獨立表示使環狀內酯開環而獲得的二價結構；R ₃係獨立表示具有碳數1以上且6以下之直鏈狀或分支鏈的伸烷基；R ₄係獨立表示氫原子或甲基)。 [5] The liquid crystal sealing agent as described in [4], wherein the curable compound (B) is a compound represented by the general formula (2): [Chem. 4]

(In the general formula (2), R ₁ represents a divalent residue derived from a polyvalent epoxy compound; R ₂ represents independently a divalent structure obtained by opening the ring of a cyclic lactone; R ₃ represents independently a A linear or branched alkylene group with a carbon number of 1 to ₆ ; R independently represents a hydrogen atom or a methyl group).

[6] Liquid crystal sealing compound as described in [4] or [5] whose content of the said curable compound (B) is 40 mass parts or more and 90 mass parts or less with respect to 100 mass parts of curable resins.

[7] The liquid crystal sealing agent according to any one of [1] to [6], which contains: a curable resin and an inorganic filler (G); Content of the said inorganic filler (G) is 20 mass parts or more and 55 mass parts or less with respect to 100 mass parts of said curable resins.

[8] The liquid crystal sealing compound according to any one of [1] to [7], wherein the moisture permeability of the cured product having a thickness of 0.6 mm in an environment of 60° C. and 90% Rh is less than 50 g/m ² .

2-2. The second aspect 2-2-1 Issues related to the second aspect As described in Patent Document 1 to Patent Document 5, in order to improve the resistance to shocks caused by dropping or the like, various studies have been made on sealants with improved flexibility after curing. Here, depending on the type of liquid crystal display panel, in order to be able to respond to bending with a smaller curvature, higher flexibility is required for the sealant. On the other hand, according to the novel knowledge of the inventors of the present invention, if the flexibility (elongation) after curing of the sealant is increased, the moisture permeability is improved, and the long-term reliability of the liquid crystal may decrease.

The second aspect of this specification is completed in view of the above-mentioned problems, and the purpose is to provide: a liquid crystal sealing agent having a cured product having high flexibility and low moisture permeability, a method of manufacturing a liquid crystal display panel using the liquid crystal sealing agent, and a liquid crystal display panel using the liquid crystal sealing agent. Liquid crystal display panels made of liquid crystal sealants.

2-2-2. Description of liquid crystal sealant The 2nd aspect of this specification relates to the liquid crystal sealing compound which has high flexibility and low moisture permeability as a cured product.

The elongation rate of the hardened product of the above sealant measured at 23°C is above 30%, and the moisture permeability of the hardened product with a thickness of 0.6mm is less than 50g/m ² at 60°C and 90Rh.

The said elongation ratio is specifically the elongation ratio measured by the following method.

Apply the sealant to a thickness of 100 μm on the release paper using a dripper. Then, put the coated sealant in a container for nitrogen replacement, and after nitrogen pressing for 5 minutes, irradiate with 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm) and heat at 120°C 1 hour to make a hardened film.

The obtained cured film was cut into thin squares (length 150mm, width 10mm), using Autograph tensile testing machine (Shimadzu Corporation, AG-X), at room temperature (23°C), according to the test speed Perform a tensile test at 10mm/min, and then calculate the stretch rate from the distance when the stress drops to more than 80% of the yield point.

The above-mentioned moisture permeability is specifically the elongation measured in accordance with the following method.

Apply the sealant to a thickness of 300 μm on the release paper using a dripper. Then, put the coated sealant in a container for nitrogen replacement, perform nitrogen pressurization for 5 minutes, irradiate with light of 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm), and heat at 120°C 1 hour to make a hardened film.

Place 2 sheets of cured film in an aluminum cup filled with moisture absorbent calcium chloride (anhydrous), place an aluminum ring and tighten the screws, then measure the initial weight of the entire aluminum cup. Then, put the aluminum cup into a constant temperature bath set at 60°C and 90% Rh, and after 24 hours, take out the aluminum cup and measure the weight. The obtained weight value was substituted into the following formula to calculate the moisture permeability. Calculation formula: Moisture permeability = (weight after test - weight before test) × film thickness / (film area × 100)

The sealant having the above moisture permeability can be prepared by various methods. For example, by using a flexible compound having an aromatic ring in the molecule or using the above-mentioned specific curable compound (B), the above-mentioned characteristics can be imparted to the sealing agent.

2-2-3. Combination of materials used in the second aspect, etc. In the liquid crystal sealing agent related to the second aspect, the above-mentioned thermosetting compound (A) having two or more epoxy groups in the molecule can also be widely used , specific curable compound (B), other curable compound (C), partial epoxy (meth)acrylate (D), thermosetting agent (E), photopolymerization initiator (F), inorganic filler ( G), and other materials. At this time, as long as the elongation rate of the cured product is more than 30% measured at 23°C, and the moisture permeability of the cured product with a thickness of 0.6mm is less than 50g/m2 under the environment of 60°C and ^90Rh , the type of resin can be properly selected. Can.

A thermosetting compound (A) can adjust various physical properties of a liquid crystal sealing compound.

It is preferable that content of a thermosetting compound (A) is 3 mass parts or more and 30 mass parts or less when the curable resin gross mass is 100 mass parts. When the content of the thermosetting compound (A) is 3 parts by mass or more, the moisture permeability of the cured product can be further reduced, and the display characteristics of the obtained liquid crystal panel can be improved. When the content of the thermosetting compound (A) is 30 parts by mass or less, the stretchability and flexibility of the cured product can be more fully improved. From the above viewpoint, the content of the thermosetting compound (A) is preferably from 10 parts by mass to 30 parts by mass, more preferably from 10 parts by mass to 25 parts by mass.

The specific hardening compound (B) adopts a round state and a stretched state of molecules in conjunction with the expansion and contraction of the sealant, which makes the expansion and contraction of the sealant easier, so that the stretchability of the hardened product can be improved, and the flexibility of the hardened product can be improved. When the substrate is bent to a smaller curvature, it is not easy to peel off and deform the hardened material. In particular, if the specific curable compound (B) is a curable compound represented by the general formula (2), the effect of easily stretching the cured product is more pronounced.

The content of the specific curable compound (B) is preferably an amount of not less than 40 parts by mass and not more than 90 parts by mass when the total mass of the curable resin is 100 parts by mass. When the above content of the specific curable compound (B) is 40 parts by mass or more, the stretchability and flexibility of the cured product can be further improved. When the said content of a specific curable compound (B) is 90 mass parts or less, the humidity resistance of hardened|cured material can be improved more, and the display characteristic of a liquid crystal panel can be improved more. From the above viewpoint, the content of the specific curable compound (B) is preferably not less than 50 parts by mass and not more than 80 parts by mass.

Other curable compounds (C) are used, for example, to provide photocurable properties to liquid crystal sealing agents using photocurable compounds. Moreover, various physical properties of a liquid crystal sealing compound can also be adjusted according to selection of another curable compound (C).

The content of other curable compounds (C) is preferably at least 0 parts by mass and less than 50 parts by mass, more preferably at least 5 parts by mass and at least 40 parts by mass, when the total mass of the curable resin is 100 parts by mass. Quantities below parts by mass.

In addition, according to the novel findings of the inventors of the present invention, a curable compound containing one (meth)acryl group in one molecule tends to be dissolved in liquid crystals, and contamination of the liquid crystals tends to occur. Therefore, from the viewpoint of liquid crystal contamination, the content of the curable compound containing one (meth)acryl group in one molecule is preferably less than 10 parts by mass when the total mass of the curable resin is 100 parts by mass. The amount is more preferably 5 parts by mass or less, particularly preferably 1 part by mass or less, and more preferably 0.1 parts by mass or less. The lower limit of the content of the curable compound containing one (meth)acryloyl group in one molecule may be 0 parts by mass.

Part of the epoxy (meth)acrylate (D) system can improve the adhesiveness of the cured product of the sealant to the substrate.

In addition, some epoxy (meth)acrylates (D) can improve the adhesiveness of the cured product, but on the other hand, it is difficult to improve the flexibility of the cured product. Therefore, from the viewpoint of further improving the flexibility of the cured product, the less the partial epoxy (meth)acrylate (D) content is, the better. From the above viewpoint, the content of a part of the epoxy (meth)acrylate (D) is preferably less than 10 parts by mass, more preferably 5 parts by mass, when the total mass of the curable resin is 100 parts by mass. The quantity of a part or less is especially preferable to be a quantity of 1 part by mass or less, and it is more preferable to be a quantity of 0.1 part by mass or less. The lower limit of the said content of some epoxy (meth)acrylates (D) can be made into 0 mass parts.

The thermosetting agent (E) is capable of curing thermosetting components such as the thermosetting compound (A), other curable compounds (C), and part of the epoxy (meth)acrylate (D).

The content of the thermosetting agent (E) is preferably not less than 3 parts by mass and not more than 75 parts by mass, more preferably not less than 3 parts by mass, based on 100 parts by mass of the total mass of the thermosetting compound (A). Moreover, the quantity of 50 mass parts or less, and the extra-premium system are the quantity of 5 mass parts or more and 40 mass parts or less. When the above content of the thermosetting agent (E) is 3 parts by mass or more, the curability of the thermosetting compound (A) can be easily improved. If the above-mentioned content of the thermosetting agent (E) is less than 75 parts by mass, the contamination of the liquid crystal due to the dissolution of the thermosetting agent (E) into the liquid crystal can be more easily suppressed.

In addition, in this aspect, by using a hydrophobic thermosetting agent that satisfies the condition that the solubility to water at 20°C is 5g/100g or less, it is possible to suppress the occurrence of bright spots (roughness) caused by applying pressure to the substrate. The system is the same as the first aspect. Also, at this time, from the viewpoint of suppressing the exudation of the thermosetting agent (E) into the liquid crystal during heat curing, when the above-mentioned liquid crystal sealing agent is heated at 25°C at 120°C, the time until G' and G'' are consistent is preferably Below 450 seconds, more preferably below 440 seconds, and extra best below 430 seconds, this is also the same as the first aspect.

The photopolymerization initiator (F) can initiate curing of specific curable compounds (B), other curable compounds (C), and some photocurable components such as epoxy (meth)acrylate (D) ( polymerization).

The content of the photopolymerization initiator (F) is the content of the photocurable compound (such as the above-mentioned partial epoxy (meth)acrylate (D), specific curable compound (B), and other curable compound (C) When the total mass is 100 parts by mass, it is preferable to be more than 0.01 parts by mass and less than 10 parts by mass. If the above-mentioned content of the photopolymerization initiator (F) is more than 0.01 parts by mass, the sealing agent can be easily increased. Curability. If the above content of the photopolymerization initiator (F) is 10 parts by mass or less, the contamination of the liquid crystal due to the dissolution of the photopolymerization initiator (F) into the liquid crystal can be more easily suppressed. The content of the starter (F) is more preferably 0.1 to 5 parts by mass, particularly preferably 0.1 to 3 parts by mass, and still more preferably 0.1 to 2.5 parts by mass.

The inorganic filler (G) not only imparts predetermined hardness and linear expansion to the cured product, but also can inhibit the penetration of water through the hardened product, so as to further reduce the moisture permeability of the cured product.

The content of the inorganic filler (G) is preferably not less than 30 parts by mass and not more than 500 parts by mass, more preferably not less than 50 parts by mass and not more than 250 parts by mass, when the total mass of the curable resin is 100 parts by mass. The following amounts are particularly preferably 70 to 200 parts by mass, more preferably 100 to 200 parts by mass. The moisture permeability of the cured product can be lowered so that the above-mentioned content of the inorganic filler (G) is larger. On the other hand, if the above-mentioned content of the inorganic filler (G) is not too much, the stretchability and flexibility of the cured product can be more fully guaranteed. From the viewpoint of obtaining such a balance, the content of the inorganic filler (G) is preferably within the above-mentioned range.

The liquid crystal sealant in this aspect may also contain: the above-mentioned thermal free radical generator, organic microparticles, coupling agents such as silane coupling agents, ion capture agents, ion exchangers, leveling agents, pigments, dyes, sensitizers, Plasticizers, and defoamers, etc.

It is preferable that content of the said thermal radical polymerization initiator shall be the quantity of 0.01 mass part or more and 5.0 weight part or less when the sealing agent gross mass is 100 weight part. By making the said content of a thermal radical polymerization initiator 0.01 mass part or more, the thermosetting property of a sealing compound can be improved more. By making the said content of a thermal radical polymerization initiator 5.0 mass parts or more, the dispensing stability of a sealant can be improved more.

It is preferable that content of the said organic fine particle shall be the quantity of 5 mass parts or more and 17 mass parts or less when the sealing agent gross mass is 100 weight part. If the content of the organic microparticles is more than 5 parts by mass, the bonding strength between the cured product and the substrate can be further improved. On the other hand, if the above-mentioned content of the organic fine particles is 17 parts by mass or less, the amount of other components (such as curable resin) can be sufficiently increased to further increase the strength of the cured product.

It is preferable that content of the said silane coupling agent shall be the quantity of 0.01 mass part or more and 5 mass parts or less when the sealing agent gross mass is 100 weight part. If the content of the silane coupling agent is more than 0.01 parts by mass, the bonding strength between the cured product and the substrate can be further improved.

The total amount of other components is preferably an amount of not less than 0.1 parts by mass and not more than 50 parts by mass when the total mass of the sealant is 100 parts by mass. If the total amount of other components is less than 50 parts by mass, the viscosity of the sealant will not be increased excessively, so that it will not be easily damaged and the coating stability of the sealant will be improved.

2-2-4. Summary of the second aspect According to the said 2nd aspect, for example, the following liquid crystal sealing compound can be provided.

[1] A liquid crystal sealing agent, which is a cured product having a elongation rate of 30% or more measured at 23°C, and a moisture permeability of the cured product with a thickness of 0.6mm under an environment of 60°C and 90Rh is less than 50g/m ² .

[2] The liquid crystal sealing agent according to [1], which contains a curable resin, and Partial epoxy (meth)acrylate (A) content is 10 mass parts or less with respect to 100 mass parts of said curable resins.

[3] The liquid crystal sealing agent as described in [1] or [2], which contains a cured compound having a property ratio of 4.70 or less, a Tg of 250°C to 340°C, and a weight average molecular weight (Mw) of 1000 or more. Active compound (B).

(一般式(1)中，R ₁係表示源自多價環氧化合物的二價殘基；R ₂係獨立表示使環狀內酯開環而獲得的二價結構；R ₃係獨立表示具有碳數1以上且6以下之直鏈狀或分支鏈的伸烷基；R ₄係獨立表示氫原子或甲基)。 [4] The liquid crystal sealing agent as described in [3], wherein the curable compound (B) is a compound represented by the general formula (2): [Chem. 5]

(In the general formula (1), R ₁ represents a divalent residue derived from a polyvalent epoxy compound; R ₂ represents independently a divalent structure obtained by opening the ring of a cyclic lactone; R ₃ represents independently a A linear or branched alkylene group with a carbon number of 1 to ₆ ; R independently represents a hydrogen atom or a methyl group).

[5] The liquid crystal sealing agent according to [4], wherein the content of the curable compound (B) represented by the general formula (1) is 40 to 90 parts by mass with respect to 100 parts by mass of the curable resin. the following.

[6] The liquid crystal sealant as described in any one of [1] to [5], which contains: a thermosetting compound having an epoxy group in the molecule (except for some epoxy (meth)acrylates) ( A), and thermosetting agent (E).

[7] The liquid crystal sealing agent as described in [6], wherein the thermosetting agent (E) is selected from: a dihydrazide-based thermolatent curing agent, an imidazole-based thermolatent curing agent, an amine adduct-based At least one kind of thermosetting agent is selected from the group consisting of a thermolatent curing agent and a polyamine-based thermolatent curing agent.

[8] The liquid crystal sealing agent according to [6] or [7], wherein the thermosetting compound (A) is a thermosetting compound having a bisphenol F skeleton in a molecule.

[9] The liquid crystal sealing agent according to any one of [1] to [8], which contains: a curable resin and an inorganic filler (G); Content of an inorganic filler (G) is 50 mass parts or more and 250 mass parts or less with respect to 100 mass parts of said curable resins.

3. Liquid crystal display panel and manufacturing method thereof A liquid crystal display panel according to another embodiment of the present invention includes: a pair of substrates (display substrate and counter substrate) each having an alignment film, a frame-shaped sealing member arranged between the alignment films of the pair of substrates, and A liquid crystal layer filled in a space surrounded by the sealing member between a pair of substrates. The said sealing member of the said liquid crystal display panel is hardened|cured material of the sealing compound (liquid crystal sealing compound) of each aspect mentioned above.

Both the display substrate and the opposite substrate are transparent substrates. The material of the transparent substrate can be inorganic materials such as glass, or plastics such as polycarbonate, polyethylene terephthalate, polyethersulfone, and PMMA.

On the surface of the display substrate or the opposite substrate, for example, matrix-shaped TFTs, color filters, black matrices, etc. can also be arranged. On the surface of the display substrate or the counter substrate, an alignment film may be further arranged. The alignment film contains known organic or inorganic alignment agents.

A liquid crystal display panel is manufactured using the liquid crystal sealing compound of this invention. The manufacturing methods of liquid crystal display panels generally include liquid crystal dropping method and liquid crystal injection method, but the liquid crystal display panel of the present invention is preferably manufactured by liquid crystal dropping method.

The manufacturing method of liquid crystal display panel according to liquid crystal dropping method includes: 1) For a pair of substrates respectively having an alignment film, coating the above-mentioned liquid crystal sealant on the alignment film of one of the substrates to form a sealing pattern; 2) When the seal pattern is in an unhardened state, drop liquid crystal on one of the substrates and in the area surrounded by the seal pattern, or on the other substrate; 3) a step of overlapping one of the substrates with the other substrate via the sealing pattern; and 4) A step of hardening the seal pattern.

In the step 2), the seal pattern is in an uncured state, which means a state in which the hardening reaction of the liquid crystal sealing agent has not progressed to the gelation point. Therefore, in the 2) step, in order to prevent the liquid crystal sealing agent from dissolving in the liquid crystal, the seal pattern may be semi-hardened by light irradiation or heating. One of the substrates and the other substrate are respectively a display substrate or a counter substrate.

4) In the step, if hardening is performed by light irradiation, then hardening by heating may also be performed thereafter. Since the liquid crystal sealing agent can be hardened in a short time by hardening by light irradiation, dissolution in liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of curing by only light irradiation.

The light to be irradiated can be appropriately selected according to the type of photopolymerization initiator (F) in the above-mentioned sealant, and is preferably light in the visible light region, for example, light with a wavelength of 370nm or more and 450nm or less. The reason is that the above-mentioned wavelength light causes less damage to the liquid crystal material and the driving electrodes. For the irradiation of light, a known light source that emits ultraviolet rays or visible light can be used. When irradiating visible light, for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, fluorescent lamps, and the like can be used.

The energy of light irradiation should just be the energy which can harden a specific curable compound (B). The photocuring time varies depending on the composition of the liquid crystal sealing agent, for example, about 10 minutes.

The thermosetting temperature varies depending on the composition of the sealant. For example, it can be set to 120°C, and the thermosetting time is about 2 hours. 50 minutes to 1.5 hours.

Furthermore, after step 4), a step of 5) applying pressure to the substrate may also be provided. The pressure treatment described above is a treatment for thinning the substrate by, for example, grinding. The conditions of the pressure treatment are not particularly limited, for example, 5 sets can be performed for 7 minutes under a load of 80N. [Example]

The present invention is described in detail according to the embodiments, but the present invention is not limited to these embodiments.

[Materials used in Examples] 1. Synthesis of specific hardening compound (B) <Synthesis Example 1: Hardening Compound (B-1)> (BisA type acrylic resin) Fill the reaction flask with: 116g of hydroxyethyl acrylate, 0.2g of p-methoxyphenol as a polymerization terminator, 148g of phthalic anhydride, and 342g of ε-caprolactone, and carry out reflux and stirring at 90°C while feeding in dry air , while reacting for 6 hours. Next, 170 g of bisphenol A diglycidyl ether was added, and it reacted for 6 hours, carrying out reflux stirring at 90 degreeC similarly. The obtained compound was washed 20 times with ultrapure water to obtain curable compound B-1.

<Synthesis Example 2: Hardening Compound (B-2)> (BisA type methacrylic resin) Fill the reaction flask with: 130g of hydroxyethyl methacrylate, 0.2g of p-methoxyphenol as a polymerization terminator, 148g of phthalic anhydride, and 342g of ε-caprolactone, and carry out the process at 90°C while feeding in dry air. The reaction was carried out for 6 hours while stirring under reflux. Next, 170 g of bisphenol A diglycidyl ether was added, and it reacted for 6 hours, carrying out reflux stirring at 90 degreeC similarly. The obtained compound was washed 20 times with ultrapure water to obtain curable compound B-2.

<Synthesis Example 3: Hardening Compound (B-3)> (BisF type acrylic resin) Fill the reaction flask with: 116g of hydroxyethyl acrylate, 0.2g of p-methoxyphenol as a polymerization terminator, 148g of phthalic anhydride, and 342g of ε-caprolactone, and carry out reflux and stirring at 90°C while feeding in dry air , while reacting for 6 hours. Next, 156 g of bisphenol F diglycidyl ether was added, and it reacted for 6 hours, carrying out reflux stirring at 90 degreeC similarly. The obtained compound was washed 20 times with ultrapure water to obtain curable compound B-3.

<Synthesis Example 4: Hardening Compound (B-4)> (BisF type methacrylic resin) Fill the reaction flask with: 130g of hydroxyethyl methacrylate, 0.2g of p-methoxyphenol as a polymerization terminator, 148g of phthalic anhydride, and 342g of ε-caprolactone, and carry out the process at 90°C while feeding in dry air. The reaction was carried out for 6 hours while stirring under reflux. Next, 156 g of bisphenol F diglycidyl ether was added, and it reacted for 6 hours, carrying out reflux stirring at 90 degreeC similarly. The obtained compound was washed 20 times with ultrapure water to obtain curable compound B-4.

2. Preparation of other materials Other materials used the following materials.

2-1. Hardening resin 2-1-1. Thermosetting compound with epoxy group in the molecule (A) ・Thermosetting compound (A-1): Propylene oxide modified bisphenol A type epoxy resin [ADEKA Co., Ltd., ADEKA RESIN EP-4000S (“ADEKA RESIN” and “ADEKA RESIN EP” are products of the same company Trademark)] ・Thermosetting compound (A-2): Bisphenol F type epoxy resin (manufactured by ADEKA Co., Ltd., ADEKA RESIN EP-4901 ・Thermosetting compound (A-3): Rubber modified (EPR modified) bisphenol F type epoxy resin (manufactured by ADEKA Co., Ltd., ADEKA RESIN EPR-4030)

2-1-2. Other hardening compounds (C) ・Other hardening compounds (C-1): Bisphenol A epoxy acrylate [DAICEL-ALLNEX Co., Ltd., EBECRYL 3700 ("EBECRYL" is a registered trademark of the same company)] ・Hardening compound (C-2): 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB)

2-1-3. Partial epoxy (meth)acrylate (D) ・Made by DAICEL-ALLNEX Co., Ltd., KRM8287 ("KRM" is a registered trademark of the same company)

2-2. Thermosetting agent 2-2-1. Thermosetting agent (E) ・Thermal curing agent (E-1): Polyamine-based thermal latent curing agent [manufactured by ADEKA Co., Ltd., EH-4357S (solubility: less than 1g/100g)] ・Thermosetting agent (E-2): imidazole-based thermolatent curing agent [manufactured by ADEKA Co., Ltd., EH-4344S (solubility: 1 g/100 g or more and 5 g/100 g or less)] ・Thermocuring agent (E-3): Dihydrazide-based thermolatent curing agent [manufactured by Nippon Seika Co., Ltd., dihydrazide adipate (ADH) (solubility: 9g/100g)] ・Thermal curing agent (E-4): Dihydrazine-based thermolatent curing agent [manufactured by Nippon Seika Co., Ltd., dihydrazine malonate (MDH) (solubility: 10g/100g)] ・Thermal curing agent (E-5): Amine adduct-based thermal latent curing agent [manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE PN-50 ("AMICURE" is a registered trademark of Ajinomoto Co., Ltd.)] ・Thermal curing agent (E-6): Dihydrazine-based thermal latent curing agent (manufactured by Ajinomoto Fine-Techno Co., Ltd., AMICURE VDH)

In addition, the solubility of thermosetting agents (E-1)-(E-4) was measured according to the method shown below.

(Measurement method of solubility) (test methods) Put 100g of water and a predetermined amount of hardener into a 300mL beaker, mix and stir for 2 hours, and judge that it is dissolved when it becomes transparent visually. Then, gradually reduce the amount of the thermosetting agent (E) added to the water. When the thermosetting agent (E) is added, mixed and stirred, and visually judged, the concentration of the thermosetting agent (E) that is judged to be dissolved for the first time is set as the above-mentioned Solubility.

2-3. Photopolymerization initiator (F) ・Photopolymerization initiator (F-1): BASF Corporation, OXE-02 ・Photopolymerization initiator (F-2): Omnipol-TX ("Omnipol" is a registered trademark of the same company) manufactured by IGM Corporation

2-4. Inorganic filler (G) ・Silicon dioxide particles: Admatechs Co., Ltd., SO-C1

2-5. Other materials ・Thermal radical generator (1): Water-soluble azo polymerization initiator (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., V-501) ・Thermal radical generator (2): Water-soluble azo polymerization initiator (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., VA-086) ・Microparticle polymer: polymethacrylate-based organic microparticles [manufactured by AICA Industry Co., Ltd., ZEFIAC F351 ("ZEFIAC" is a registered trademark of Japan ZEON Co., Ltd.)] ・Silane coupling agent: Shin-Etsu Chemical Co., Ltd., KBM403

2-6. Physical properties of each material The weight average molecular weight (Mw) of each resin component mentioned above was calculated|required using the gel permeation chromatography (GPC).

In addition, the epoxy equivalent of the resin component which has an epoxy group was calculated|required based on JISK7236 (2001).

In addition, the property ratio and glass transition temperature (Tg) of each resin component mentioned above were calculated|required by the Bicerano method using the calculation software Materials Studio 2020 Synthia.

The above physical properties are shown in Table 1.

[Table 1] Abbreviation name mw Epoxy equivalent (g/eq) characteristic ratio Tg (℃) A-1 ADEKA RESIN EP-4000S 520 260 A-2 ADEKA RESIN EP-4901 340 170 A-3 ADEKA RESIN EPR-4030 730 365 B-1 Hardening compound B-1 1451 - 4.37 305 B-2 Hardening compound B-2 1479 - 4.33 305 B-3 Hardening compound B-3 1423 - 4.41 287 B-4 Hardening compound B-4 1451 - 4.37 287 C-1 EBECRYL 3700 485 - 4.33 352 C-2 2-Hydroxybutyl methacrylate - D. KRM8287

[Examples and comparative examples related to the first aspect] 1-1. Preparation of sealant 80 mass parts of thermosetting compound (A-1), 520 mass parts of curable compound (B-1), 60 mass parts of other curable compounds (C-1), 80 mass parts of thermosetting agent ( E-1), 5 parts by mass of photopolymerization initiator (F-1), 175 parts by mass of silica particles, 70 parts by mass of microparticle polymer, and 10 parts by mass of silane coupling agent, using a three-roll machine Mix well to form a homogeneous solution to obtain a sealant (1).

Except that the type and blending amount of the materials used were changed as described in Table 2 to Table 4, the sealant (2) to sealant (14) were obtained in the same way.

The compositions of sealant (1) to sealant (14) are shown in Table 2 to Table 4. In addition, the numerical value described about each component represents a mass part unless otherwise stated.

1-2. Evaluation For the sealants (1) to (14) prepared above, Young's modulus, elongation at break, drop characteristics, moisture permeability, display characteristics, low temperature curability, and coating properties were evaluated according to the following methods .

<Young's modulus> The obtained sealant was applied on a release paper to a thickness of 100 μm using a dripper. Then, put the coated sealant in a container for nitrogen replacement, perform nitrogen pressurization for 5 minutes, irradiate with 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm) and heat at 120°C for 1 Hours to make a hardened film.

The obtained cured film was cut into thin squares (length 150mm, width 10mm), using Autograph tensile testing machine (Shimadzu Corporation, AG-X), at room temperature (23°C), according to the test speed Tensile test was performed at 10mm/min, and Young's modulus was calculated from the slope of stress and strain in the elastic region.

<Falling characteristics> The obtained sealant was formed on a 140mm×70mm glass substrate (RT-DM88-PIN, manufactured by EHC Corporation) on which a transparent electrode and an alignment film were previously formed using a dispenser (SHOTMASTER, manufactured by Musashi Engineering Co., Ltd.). 135mm×65mm square seal pattern of the main seal (cross-sectional area 3500μm ² ).

Next, a liquid crystal material (MLC-6609-000, manufactured by Merck) corresponding to the content of the bonded panel was precisely dropped in the frame of the main seal using a dispenser. Then, after bonding the paired glass substrates under reduced pressure, the atmosphere was released and bonded. Then, after keeping the bonded two glass substrates in a light-shielding box for 1 minute, in a state where only the liquid crystal portion is covered by the substrate coated with a black matrix, irradiate light containing 3000 mJ/cm ² of visible light (wavelength 370 ~450nm light), and heated at 120°C for 1 hour to harden the main seal to obtain a liquid crystal display panel.

The obtained liquid crystal display panel was dropped from a height of 50 mm. When the panel did not peel off or the liquid crystal leaked due to cracking, the drop position was raised 50 mm each time and the drop test was repeated. The upper limit of the height was set at 500 mm. The panel after the test was visually observed, and the drop characteristics were evaluated according to the following criteria. ◎: Up to 500mm, there was no peeling of the panel or liquid crystal leakage due to cracking ○: When the height is more than 300mm and less than 500mm, liquid crystal leakage occurs on the liquid crystal display panel ×: When the height is less than 300mm, liquid crystal leakage occurs on the liquid crystal display panel

<Moisture permeability> The obtained sealant was applied on a release paper to a thickness of 300 μm using a dripper. Then, put the coated sealant in a container for nitrogen replacement, perform nitrogen pressurization for 5 minutes, irradiate with light of 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm), and heat at 120°C 1 hour to make a hardened film.

Place 2 sheets of cured film in an aluminum cup filled with moisture absorbent calcium chloride (anhydrous), place an aluminum ring and tighten the screws, then measure the initial weight of the entire aluminum cup. Then, put the aluminum cup into a constant temperature bath set at 60°C and 90% Rh, and after 24 hours, take out the aluminum cup and measure the weight. The obtained weight value was substituted into the following formula to calculate the moisture permeability. Calculation formula: Moisture permeability = (weight after test - weight before test) × film thickness / (film area × 100)

<Display characteristics (suppression of roughness)> Using a dispenser (SHOTMASTER, manufactured by Musashi Engineering Co., Ltd.), the obtained sealant was placed on a 40mm×45mm glass substrate (manufactured by EHC Co., Ltd.) on which a transparent electrode and a hard film were formed. , RT-DM88-PIN), form a 35mm×35mm square seal pattern of the main seal (cross-sectional area of 3500μm ² ), and a 38mm×38mm square seal pattern on the periphery.

Next, liquid crystal material (MLC-7026-100, manufactured by Merck Co., Ltd.) equivalent to the liquid crystal content of the liquid crystal display panel to be obtained was precisely dropped in the main seal frame using a dispenser, and then left to stand for 100 minutes or 10 minutes. Then, after bonding the paired glass substrates under reduced pressure, the atmosphere was released and bonded. Then, the above-mentioned glass substrate and the glass substrate paired with the above-mentioned glass substrate were bonded under a reduced pressure of 4 Pa, and then released to atmospheric pressure. After the bonded two glass substrates are kept in the light-shielding box for 1 minute, the main seal is covered with a substrate that has formed a 36mm×36mm square black matrix. In this state, the glass substrate is irradiated with a wavelength of 370 at 1J/ ^cm2 ~450nm light. Furthermore, these glass substrates were heated at 120 degreeC for 1 hour, the main seal was hardened, and the liquid crystal panel was obtained. Then, a polarizing film is pasted on both sides of the obtained liquid crystal panel to obtain a liquid crystal display panel. The obtained liquid crystal display panel was pressurized at 80N for 10 minutes.

The display characteristics of the obtained liquid crystal panel were evaluated according to the following criteria. ⊚: There were no bright spots (roughness) in the case of standing still for 100 minutes and the case of standing still for 10 minutes. ◯: Bright spots (roughness) were observed in the case of standing for 100 minutes, but no bright spots (roughness) were observed in the case of standing for 10 minutes. ×: Bright spots (roughness) were observed in both those who left still for 100 minutes and those who left still for 10 minutes.

＜Low temperature curing＞ While measuring the storage elastic modulus (G') and loss elastic modulus (G'') with a dynamic viscoelasticity measuring device (rheometer), the 25°C sealant is placed in an environment of 120°C (constant temperature) and implemented. heating. At this time, the time from the start of heating until G' and G'' coincided was measured.

The Young's modulus, drop characteristics, moisture permeability, display characteristics, and evaluation results of the sealant (1) to sealant (14) are shown in Table 2 to Table 4. In addition, in the table, the amount of the thermosetting compound (A) having an epoxy group in the molecule relative to the total mass of the curable resin (column "(A) amount/total curable resin"), relative to the cured The amount of the specific curable compound (B) in the total mass of the curable resin (column "(B) amount/total curable resin"), and the part of the epoxy (a Base) Acrylate (D) amount (column "(D) amount/total curable resin").

[Table 2] Sealant No. (1) (2) (3) (4) (5) (6) (7) Example Example Example Example Example Example Example composition Thermosetting compound (A) A-1 80 50 50 80 80 80 A-2 100 A-3 Hardening compound (B) B-1 520 550 500 500 B-2 520 B-3 520 B-4 520 Hardening compound (C) C-1 60 60 60 60 60 60 60 Partial epoxy (meth)acrylate (D) 50 Thermohardener (E) E-1 80 80 80 80 80 80 80 E-2 E-3 E-4 Photopolymerization initiator (F) F-1 5 5 5 5 5 5 5 F-2 Inorganic filler (G) 175 175 175 175 175 175 175 thermal free radical generator (1) microparticle polymer 70 70 70 70 70 70 70 Silane coupling agent 10 10 10 10 10 10 10 (A) amount/total curable resin 12.12% 7.58% 15.15% 7.58% 12.12% 12.12% 12.12% (B) amount/total curable resin 78.79% 83.33% 75.76% 75.76% 78.79% 78.79% 78.79% (D) amount/total curable resin 0.00% 0.00% 0.00% 7.58% 0.00% 0.00% 0.00% result Young's modulus (%) 0.8 0.7 0.6 1.2 0.9 0.6 0.7 drop resistance ○ ○ ○ ○ ○ ○ ○ Moisture permeability (g/m ² ) 42 44 44 41 41 44 43 Display characteristics (roughness suppression) ◎ ◎ ◎ ◎ ◎ ◎ 〇 low temperature hardening 395 385 400 395 395 395 395

[table 3] Sealant No. (8) (9) (10) Example Example Example composition Thermosetting compound (A) A-1 150 80 80 A-2 A-3 Hardening compound (B) B-1 500 520 520 B-2 B-3 B-4 Hardening compound (C) C-1 70 60 60 Partial epoxy (meth)acrylate (D) Thermohardener (E) E-1 80 80 E-2 20 E-3 E-4 Photopolymerization initiator (F) F-1 5 5 F-2 5 Inorganic filler (G) 175 165 175 thermal free radical generator (1) 10 microparticle polymer 70 70 70 Silane coupling agent 10 10 10 (A) amount/total curable resin 20.83% 12.12% 12.12% (B) amount/total curable resin 69.44% 78.79% 78.79% (D) amount/total curable resin 0.00% 0.00% 0.00% result Young's modulus (%) 1.1 0.9 0.8 drop resistance ○ ○ ○ Moisture permeability (g/m ² ) 41 41 43 Display characteristics (roughness suppression) 〇 〇 〇 low temperature hardening 390 330 395

[Table 4] Sealant No. (11) (12) (13) (14) Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 composition Thermosetting compound (A) A-1 30 100 150 150 A-2 A-3 Hardening compound (B) B-1 460 60 490 490 B-2 B-3 B-4 Hardening compound (C) C-1 500 80 80 Partial epoxy (meth)acrylate (D) 250 Thermohardener (E) E-1 50 80 E-2 E-3 20 E-4 20 Photopolymerization initiator (F) F-1 5 5 5 5 F-2 Inorganic filler (G) 175 175 175 175 thermal free radical generator (1) microparticle polymer 20 70 70 70 Silane coupling agent 10 10 10 10 (A) amount/total curable resin 4.05% 15.15% 20.83% 20.83% (B) amount/total curable resin 62.16% 9.09% 68.06% 68.06% (D) amount/total curable resin 33.78% 0.00% 0.00% 0.00% result Young's modulus (%) 3.0 3.6 0.6 0.7 drop resistance x x 〇 〇 Moisture permeability (g/m ² ) 39 26 46 45 Display characteristics (roughness suppression) ○ 〇 x x low temperature hardening 425 400 470 505

From Table 2 to Table 4, it can be seen that by using a thermosetting compound (A) containing epoxy groups in the molecule and having a Young's modulus of 0.5 GPa or more and less than 3.0 GPa measured at 23°C, and thermosetting agent (E), and the above-mentioned thermosetting agent (E) is a liquid crystal sealing compound of a thermosetting agent whose solubility in water at 20°C is below 5g/100g, and can suppress the occurrence of bright spots (rough ).

[Examples and comparative examples related to the second aspect] 2-1. Preparation of sealant 80 mass parts of thermosetting compound (A-1), 520 mass parts of curable compound (B-1), 120 mass parts of other curable compounds (C-1), 20 mass parts of thermosetting agent ( E-5), 5 parts by mass of photopolymerization initiator (F-1), 175 parts by mass of silica particles, 70 parts by mass of microparticle polymer, and 10 parts by mass of silane coupling agent, using a three-roll machine Mix well to form a homogeneous solution to obtain a sealant (21).

Except for changing the type and blending amount of the materials used as described in Table 5 and Table 6, the sealant (22) to sealant (33) were obtained in the same way.

The composition of sealant (21) ~ sealant (33) is shown in Table 5 and Table 6. In addition, the numerical values described in the relevant components all represent "parts by mass" unless otherwise stated.

2-2. Evaluation About the sealant (21) - sealant (33) prepared above, elongation, flexibility, moisture permeability, and liquid crystal contamination were evaluated by the following methods.

<Elongation ratio> The obtained sealant was applied on a release paper to a thickness of 100 μm using a dripper. Then, put the coated sealant in a container for nitrogen replacement, perform nitrogen pressurization for 5 minutes, irradiate with 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm) and heat at 120°C for 1 Hours to make a hardened film.

The obtained cured film was cut into thin squares (length 150mm, width 10mm), using Autograph tensile testing machine (Shimadzu Corporation, AG-X), at room temperature (23°C), according to the test speed Perform a tensile test at 10mm/min, and then calculate the stretch rate from the distance when the stress drops to more than 80% of the yield point.

＜flexibility＞ The obtained cured film was cut into a thin square shape (length 50 mm, width 10 mm), bent along a mandrel with a diameter of 1.0 mm or 1.5 mm, and fixed for 10 seconds. Remove the hardened film from the mandrel and let it rest on a flat table for 1 minute. Then, the state of the cured film was visually observed, and flexibility was evaluated according to the following criteria. ◎: For mandrels with a diameter of 1.0 mm and a diameter of 1.5 mm, there is no deformation such as cracking or bending ○: Although the mandrel with a diameter of 1.0mm has deformation such as bending, there is no deformation such as cracking or bending for the mandrel with a diameter of 1.5mm △: Although there is no crack in the mandrel with a diameter of 1.5mm, there is deformation such as bending ×: Cracks occurred on the mandrel with a diameter of 1.5mm

<Moisture permeability> The obtained sealant was applied on a release paper to a thickness of 300 μm using a dripper. Then, put the coated sealant in a container for nitrogen replacement, perform nitrogen pressurization for 5 minutes, irradiate with 3000mJ/cm ² (light corrected by a sensor with a wavelength of 365nm) and heat at 120°C for 1 Hours to make a hardened film.

Place 2 sheets of cured film in an aluminum cup filled with moisture absorbent calcium chloride (anhydrous), place an aluminum ring and tighten the screws, then measure the initial weight of the entire aluminum cup. Then, put the aluminum cup into a constant temperature bath set at 60°C and 90% Rh, and after 24 hours, take out the aluminum cup and measure the weight. The obtained weight value was substituted into the following formula to calculate the moisture permeability. Calculation formula: Moisture permeability = (weight after test - weight before test) × film thickness / (film area × 100)

＜Contamination of liquid crystal＞ 0.03 g of the obtained sealing agent and 0.3 g of liquid crystals (manufactured by Merck, MLC-7026-100) were weighed in a 1 ml beaker, and it heated at 120 degreeC for 1 hr. The nematic-isotropic liquid phase transition temperature (NI point) of the contaminated liquid crystal due to heating is compared with the NI point of the uncontaminated liquid crystal before heating, and the difference (ΔNI point) is calculated. Moreover, when using the liquid crystal sealing compound with low liquid-crystal contamination property, the absolute value of ΔNI point will become small. The obtained ΔNI points were also evaluated for the sealant according to the following criteria. 〇: ΔNI point is within 2.0°C ×: ΔNI point greater than 2.0°C

Table 5 and Table 6 show the evaluation results of elongation, flexibility, moisture permeability, and liquid crystal contamination of sealant (22) to sealant (33). In addition, the table indicates: relative to the total mass of the curable resin, the amount of the thermosetting compound (A) with epoxy groups in the molecule (column "(A) amount/total curable resin"), relative to the curable The amount of specific hardening compound (B) in the total mass of resin (column "(B) amount / total hardening resin"), and the part of epoxy (meth)acrylate (D ) amount (“(D) amount/total curable resin” field).

[table 5] Sealant No. (twenty one) (twenty two) (twenty three) (twenty four) (25) (26) (27) Example Example Example Example Example Example Example composition Thermosetting compound (A) (A-1) 80 50 50 80 80 80 (A-2) 80 Hardening compound (B) (B-1) 520 550 520 500 (B-2) 520 (B-3) 520 (B-4) 520 Hardening compound (C) (C-1) 120 120 120 120 120 120 120 (C-2) Partial epoxy (meth)acrylate (D) 50 Thermohardener (E) (E-5) 20 20 20 20 20 20 20 (E-6) Photopolymerization initiator (F) (F-1) 5 5 5 5 5 5 5 (F-2) Inorganic filler (G) 175 175 175 175 175 175 175 thermal free radical generator (2) microparticle polymer 70 70 70 70 70 70 70 Silane coupling agent 10 10 10 10 10 10 10 (A) amount/total curable resin 11.11% 6.94% 11.11% 6.94% 11.11% 11.11% 11.11% (B) amount/total curable resin 72.22% 76.39% 72.22% 69.44% 72.22% 72.22% 72.22% (D) amount/total curable resin 0.00% 0.00% 0.00% 6.94% 0.00% 0.00% 0.00% result Elongation (%) 38 39 41 35 37 42 41 flexibility ○ ○ ◎ 〇 〇 ◎ ◎ Moisture permeability (g/m ² ) 41 43 44 39 40 44 43 Liquid crystal contamination 〇 〇 〇 〇 〇 〇 〇

[Table 6] Sealant No. (28) (29) (30) (31) (32) (33) Example Example Example comparative example comparative example comparative example composition Thermosetting compound (A) (A-1) 80 80 80 30 150 50 (A-2) Hardening compound (B) (B-1) 520 520 520 460 250 500 (B-2) (B-3) (B-4) Hardening compound (C) (C-1) 120 120 120 320 50 (C-2) 120 Partial epoxy (meth)acrylate (D) 250 Thermohardener (E) (E-5) 20 20 20 20 20 (E-6) 20 Photopolymerization initiator (F) (F-1) 5 5 5 5 5 (F-2) 5 Inorganic filler (G) 175 165 175 175 175 175 thermal free radical generator (2) 10 microparticle polymer 70 70 70 50 70 70 Silane coupling agent 10 10 10 10 10 10 (A) amount/total curable resin 11.11% 11.11% 11.11% 4.05% 20.83% 6.94% (B) amount/total curable resin 72.22% 72.22% 72.22% 62.16% 34.72% 69.44% (D) amount/total curable resin 0.00% 0.00% 0.00% 33.78% 0.00% 0.00% result Elongation (%) 38 38 39 11 4 28 flexibility ○ ○ ○ x x △ Moisture permeability (g/m ² ) 44 40 42 41 33 47 Liquid crystal contamination 〇 〇 〇 ○ 〇 x

It is known from Table 5 and Table 6 that according to the liquid crystal sealing agent of the present invention, both high flexibility and low moisture permeability can be achieved.

This application is based on Japanese application No. 2021-046327 filed on March 19, 2021, Japanese application No. 2021-046329 filed on March 19, 2021, and March 19, 2021 Japanese application Japanese Patent Application No. 2021-046333 of the filed application claims priority. Reference is made to the descriptions, patent claims, and abstracts of these applications, and they are incorporated by reference in this application. (industrial availability)

The present invention is very useful for the application of various liquid crystal display panels.

Claims (14)

A liquid crystal sealant, the Young's modulus measured at 23°C of the cured product is more than 0.5GPa and less than 3.0GPa, which contains: A thermosetting compound (A) having an epoxy group in the molecule, and Thermohardener (E); Among them, the above-mentioned thermosetting agent (E) is a thermosetting agent having a solubility in water at 20° C. of 5 g/100 g or less. The liquid crystal sealing agent according to claim 1, wherein the thermosetting agent (E) is composed of an imidazole-based thermolatent curing agent, an amine adduct-based thermolatent curing agent, and a polyamine-based thermolatent curing agent Select at least one thermohardener from the group. Such as the liquid crystal sealant of claim 1 or 2, wherein, while using a dynamic viscoelasticity measuring device (rheometer) to measure the storage elastic modulus (G') and the loss elastic modulus (G''), the 25°C When the said liquid crystal sealing compound heats at 120 degreeC, the time until G' and G'' match is 450 seconds or less. The liquid crystal sealing agent according to claim 1 or 2, which contains a curable compound (B) having a property ratio of 4.70 or less, a Tg of 250° C. to 340° C., and a weight average molecular weight (Mw) of 1000 or more. Such as the liquid crystal sealing agent of claim 4, wherein, the above-mentioned curable compound (B) is a compound shown in general formula (2): [Chemical 1]

(In the general formula (2), R ₁ represents a divalent residue derived from a polyvalent epoxy compound; R ₂ represents independently a divalent structure obtained by opening the ring of a cyclic lactone; R ₃ represents independently a A linear or branched alkylene group with a carbon number of 1 to ₆ ; R independently represents a hydrogen atom or a methyl group). The liquid crystal sealing compound of Claim 4 whose content of the said curable compound (B) is 40 mass parts or more and 90 mass parts or less with respect to 100 mass parts of curable resins. Such as the liquid crystal sealant of claim 1 or 2, which contains: curable resin and inorganic filler (G); Content of the said inorganic filler (G) is 20 mass parts or more and 55 mass parts or less with respect to 100 mass parts of said curable resins. The liquid crystal sealing compound according to claim 1 or 2, wherein the moisture permeability of the hardened product with a thickness of 0.6 mm under the environment of 60° C. and 90% Rh is less than 50 g/m ² . A method of manufacturing a liquid crystal display panel, comprising: For a pair of substrates respectively having an alignment film, coating the liquid crystal sealant of any one of claims 1 to 8 on the alignment film of one of the substrates to form a sealing pattern; A step of dropping liquid crystals on one of the above-mentioned substrates and in the area of the above-mentioned seal pattern, or on the other substrate, in the unhardened state of the above-mentioned seal pattern; a step of overlapping one of the substrates with the other substrate via the sealing pattern; and A step of hardening the above seal pattern. The method of manufacturing a liquid crystal display panel according to claim 9, wherein in the step of hardening the seal pattern, the seal pattern is irradiated with light to harden the seal pattern. The method of manufacturing a liquid crystal display panel according to claim 10, wherein the light irradiated on the seal pattern includes light in the visible light range. The method of manufacturing a liquid crystal display panel according to claim 10 or 11, wherein in the step of hardening the seal pattern, the seal pattern irradiated with light is further heated. The method for manufacturing a liquid crystal display panel according to claim 9 or 10, further comprising: after the step of hardening the seal pattern, applying pressure to the substrate. A liquid crystal display panel comprising: a pair of substrates respectively having an alignment film; a frame-shaped sealing member disposed between the alignment films of the pair of substrates; and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates; In addition, the said sealing member is the hardened|cured material of the liquid crystal sealing compound in any one of Claims 1-8.