JP2017040763A - Sealant for display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant for display elements that has excellent adhesiveness and transparency, and can suppress outgassing and gelation when coming in contact with metal.SOLUTION: A sealant for display elements comprises a polymerizable compound comprising a polythiol monomer having three or more thiol groups in one molecule and a polyene monomer having three or more carbon-carbon double bonds in one molecule, a polymerization initiator, a phenolic stabilizer, and a carbodiimide compound.SELECTED DRAWING: None

Description

The present invention relates to a sealant for a display element that is excellent in adhesiveness and transparency, and that can suppress generation of outgas and gelation when contacted with a metal.

In recent years, liquid crystal display elements, organic EL display elements, and the like are widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is usually used for sealing a liquid crystal or a light emitting layer.

A liquid crystal display element usually has two transparent substrates with electrodes facing each other at a predetermined interval, and the periphery thereof is sealed with a sealant to form a cell, and a liquid crystal injection port provided in a part thereof Then, liquid crystal is injected into the cell, and the liquid crystal injection port is sealed with a liquid crystal display element sealing agent. Conventionally, as a sealing agent for liquid crystal display elements, a photocurable acrylic resin composition or the like as described in Patent Document 1 has been widely used. The photo-curable acrylic resin composition is excellent in workability and productivity, but because of its strong interaction with the liquid crystal, it contaminates the liquid crystal and causes color unevenness or remains in the manufacturing process of the display element. There was a problem that a large amount of outgas was generated by the acrylic resin, or the adhesiveness and transparency of the cured product were inferior.

In addition, in the organic EL display element, when the organic light emitting material layer and the electrode are exposed to the outside air, the performance of the organic EL display element deteriorates rapidly. Therefore, in order to increase the stability and durability of the organic EL display element, There has been proposed a method in which a material layer and an electrode are covered with a resin film via an inorganic material film and sealed. For example, Patent Document 2 discloses a method of forming a resin film made of an acrylic resin composition on an inorganic material film. Patent Document 3 also discloses a method based on photocationic polymerization. However, even in such a case, there are problems such as outgas generation.

JP-A-6-160972 JP 2001-307873 A JP 2005-336314 A

An object of this invention is to provide the sealing agent for display elements which is excellent in adhesiveness and transparency, and can suppress generation | occurrence | production of an outgas and gelatinization at the time of contacting with a metal.

The present invention relates to a polythiol monomer having three or more thiol groups in one molecule, a polymerizable compound containing a polyene monomer having three or more carbon-carbon double bonds in one molecule, and a polymerization initiator. And a phenolic stabilizer and a carbodiimide compound.
The present invention is described in detail below.

Since the sealing agent for display elements needs durability by a wet heat resistance test, it is required to have a high glass transition temperature. Therefore, the present inventors use a polythiol monomer having three or more thiol groups in one molecule and a polyene monomer having three or more carbon-carbon double bonds in one molecule as the polymerizable compound. Therefore, it was studied to produce a sealant for a display element that exhibits a high glass transition temperature, is excellent in adhesiveness and transparency, and can suppress outgassing. However, the obtained sealant for a display element has a problem that it easily gels when it comes into contact with a metal such as stainless steel or iron widely used for piping materials and containers.
Therefore, as a result of intensive studies, the present inventors have found that gelation at the time of contact with a metal can be suppressed by further combining a phenol-based stabilizer and a carbodiimide compound, thereby completing the present invention. It came to.
The sealant for display element of the present invention can further prevent the occurrence of liquid crystal contamination when used in a liquid crystal display element and damage to the organic light emitting material layer when used in an organic EL display element.
In the present specification, the “display element” represents a liquid crystal display element and an organic EL display element.

The sealant for display elements of the present invention contains a phenol-based stabilizer.
By containing the phenol-based stabilizer in combination with a carbodiimide compound described later, the sealant for display element of the present invention is excellent in the effect of suppressing gelation when it comes into contact with a metal.
Moreover, the said phenol-type stabilizer also has effects, such as antioxidant.

As the phenol-based stabilizer, a hindered phenol-based stabilizer is preferable from the viewpoint of better suppressing gelation upon contact with a metal, and specifically, for example, 2,2′-methylenebis- (4-methyl). -6-tert-butylphenol), 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol) and the like. . Of these, 2,2'-methylenebis- (4-methyl-6-t-butylphenol) is preferable. These phenolic stabilizers may be used alone or in combination of two or more.

The content of the phenol stabilizer is preferably 0.2 parts by weight and preferably 3.0 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the above-mentioned phenol-based stabilizer is within this range, the resulting sealant for display element is gelled when it comes into contact with metal while maintaining excellent curability and the effect of suppressing outgassing. It will be excellent by the effect which suppresses. The minimum with more preferable content of the said phenol type stabilizer is 0.4 weight part, and a more preferable upper limit is 1.5 weight part.

The sealing agent for display elements of this invention contains a carbodiimide compound.
As described above, by containing the carbodiimide compound in combination with the phenol-based stabilizer, the sealant for display element of the present invention is excellent in the effect of suppressing gelation when contacting with a metal. .
Moreover, the sealing agent for display elements of this invention is excellent also in the reliability in a high-temperature, high-humidity environment by containing the said carbodiimide compound.

Examples of the carbodiimide compound include 1,3-diisopropylcarbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and 1- (3- (dimethyl Amino) propyl) -3-ethylcarbodiimide, N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, N-cyclohexyl-N ′-(2-morpholinoethyl) carbodiimidemeth-p-toluenesulfonate, terminal Examples include isocyanate group-modified polycarbodiimide compounds, cyclic carbodiimide compounds, and polycarbodiimide compounds obtained by polymerizing diisocyanate in the presence of a carbodiimidization catalyst. Especially, a polycarbodiimide compound and a cyclic carbodiimide compound are preferable from a viewpoint of suppressing generation | occurrence | production of an outgas.
Examples of the commercially available polycarbodiimide compounds include carbodilite V02B, carbodilite V04K, carbodilite V05 (all manufactured by Nisshinbo Co., Ltd.), and the like, among the cyclic carbodiimide compounds, For example, cyclic carbodiimide (manufactured by Teijin Ltd.) and the like can be mentioned.

The content of the carbodiimide compound is preferably 0.01 parts by weight and preferably 2.0 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the carbodiimide compound is within this range, the resulting sealant for display elements suppresses gelation when in contact with metal while maintaining excellent curability and the effect of suppressing generation of outgas. It will be superior to the effect of doing. The minimum with more preferable content of the said carbodiimide compound is 0.1 weight part, and a more preferable upper limit is 1.0 weight part.

The sealant for a display element of the present invention includes, as a polymerizable compound, a polythiol monomer having 3 or more thiol groups in one molecule (hereinafter also referred to as “trifunctional or more polythiol monomer”), and 1 molecule. Contains a polyene monomer having three or more carbon-carbon double bonds (hereinafter also referred to as “a triene or more polyene monomer”). The sealant for display elements of the present invention containing these components as the polymerizable compound is excellent in adhesiveness, transparency, and the effect of suppressing the generation of outgas.
In the present specification, the “carbon-carbon double bond” means an ethylenically unsaturated bond.

Examples of the tri- or higher functional polythiol monomer include tris (3-mercaptopropionyloxy) ethyl isocyanurate, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), and tris. Methylolpropane tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione , Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, dipentaerythritol hexakis (3-mercaptopropionate), dipenta Lithritol hexakis (3-mercaptobutyrate), 4- (mercaptomethyl) -3,6-dithiaoctane-1,8-dithiol, 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane -1,11-dithiol, 4,8-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis (mercaptomethyl) -3,6,9-tri Examples include thiaundecane-1,11-dithiol. These trifunctional or higher functional polythiol monomers may be used alone or in combination of two or more.

Among the above-described trifunctional or higher functional polythiol monomers, an ester bond-containing polythiol compound is preferable because the obtained sealant for display element is excellent in transparency.

Specific examples of the ester bond-containing polythiol compound include tris (3-mercaptopropionyloxy) ethyl isocyanurate, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate). ), Trimethylolpropane tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trione, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, dipentaerythritol hexakis (3-mercaptopropionate) , Dipentaerythritol hexakis (3-mercapto butyrate), and the like.
Among them, trimethylolpropane tris (3-mercaptopropionate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3 -Mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol Hexakis (3-mercapto butyrate) is more preferable.

The tri- or higher functional polythiol monomer preferably has 4 or more thiol groups in one molecule, more preferably 4 to 20 thiol groups in one molecule, and more preferably 4 in one molecule. More preferably, it has ˜8 thiol groups.

Specific examples of the polythiol monomer having four or more thiol groups in one molecule include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and pentaerythritol tetrakisthiol. Glycolate, dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane- 1,11-dithiol, 4,8-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis (mercaptomethyl) -3,6,9-trithia And undecane-1,11-dithiol. Of these, pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptobutyrate) are preferable.

Since the above-mentioned trithiol or higher polythiol monomer is excellent in the effect of suppressing gelation when it comes into contact with a metal, a polythiol monomer having a secondary thiol group (hereinafter referred to as “trifunctional or higher functionality having a secondary thiol group”). It is preferable to contain a polythiol monomer.
The tri- or higher functional polythiol monomer having the secondary thiol group may have all thiol groups that are secondary thiol groups or only some thiol groups may be secondary thiol groups. .

In addition to the above trifunctional or higher functional polythiol monomer, the polymerizable compound may be a polythiol monomer having two thiol groups in one molecule (hereinafter referred to as “bifunctional polythiol”). Also referred to as "monomer").
Hereinafter, a polythiol monomer having two or more thiol groups in one molecule is also simply referred to as “polythiol monomer”.

When the bifunctional polythiol monomer is contained, the preferable lower limit of the content ratio of the trifunctional or higher polythiol monomer in 100 parts by weight of the whole polythiol monomer is 70 parts by weight, and the preferable upper limit is 98 parts by weight. When the content ratio of the trifunctional or higher polythiol monomer is within this range, the obtained sealant for display element is more excellent in the effect of suppressing the generation of outgas, adhesiveness, and curability. The more preferable lower limit of the content ratio of the trifunctional or higher polythiol monomer is 80 parts by weight, and the more preferable upper limit is 95 parts by weight.

Examples of the trifunctional or higher polyene monomer include (meth) allyl compounds and (meth) acrylic compounds. These polyene monomers may be used alone or in combination of two or more.
In the present specification, the “(meth) allyl” means allyl or methallyl, and the “(meth) acryl” means acryl or methacryl.

Examples of the (meth) allyl compound include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, triallyl trimellitate, tetraallyl pyromellitate, pentaerythritol triallyl ether, and the like. Of these, triallyl cyanurate and triallyl isocyanurate are preferable.

The (meth) acrylic compound is not particularly limited as long as it is a compound having three or more (meth) acryloyl groups in one molecule. For example, an epoxy obtained by reaction of (meth) acrylic acid and an epoxy compound ( Examples include ester compounds obtained by reacting a compound having a hydroxyl group with (meth) acrylate and (meth) acrylic acid.
In the present specification, “(meth) acryloyl” means acryloyl or methacryloyl, “(meth) acrylate” means acrylate or methacrylate, and “epoxy (meth) acrylate” Represents a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.

The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy compound in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound used as a raw material for the epoxy (meth) acrylate include, for example, a sulfphenol novolak type epoxy compound, an orthocresol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, a biphenyl novolac type epoxy compound, and a naphthalenephenol novolak type epoxy. Compounds, glycidylamine type epoxy compounds, and the like.

Examples of the ester compound include trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, and caprolactone-modified trimethylolpropane tri (meth). ) Acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Rupenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

The trifunctional or higher polyene monomer preferably has 4 or more carbon-carbon double bonds in one molecule, and preferably has 4 to 20 carbon-carbon double bonds in one molecule. More preferably, it has 4-8 carbon-carbon double bonds in one molecule.

The polymerizable compound is a polyene monomer having two carbon-carbon double bonds in one molecule (hereinafter referred to as “bifunctional”) in addition to the above-mentioned triene or higher polyene monomer as long as the object of the present invention is not impaired. Of polyene monomer).
Hereinafter, a polyene monomer having two or more carbon-carbon double bonds in one molecule is also simply referred to as “polyene monomer”.

When the bifunctional polyene monomer is contained, the preferable lower limit of the content ratio of the trifunctional or higher polyene monomer in 100 parts by weight of the whole polyene monomer is 70 parts by weight, and the preferable upper limit is 98 parts by weight. When the content ratio of the trifunctional or higher polyene monomer is within this range, the obtained sealant for display element is more excellent in the effect of suppressing generation of outgas, adhesiveness, and curability. The minimum with more preferable content rate of the said polyfunctional monomer more than trifunctional is 80 weight part, and a more preferable upper limit is 95 weight part.

As the blending ratio of the polythiol monomer and the polyene monomer, the ratio of the thiol group of the polythiol monomer and the carbon-carbon double bond of the polyene monomer is a molar ratio, thiol group: carbon-carbon double bond = It is preferable to mix | blend in the range used as 3: 1 to 1: 3, and it is more preferable to mix | blend in the range used as thiol group: carbon-carbon double bond = 2: 1 to 1: 2.

From the viewpoint of reliability in a high-temperature and high-humidity environment, the sealant for display elements of the present invention is a reactive functional group (hereinafter simply referred to as “reactive functional group”) that can react with the polythiol monomer and / or the polyene monomer. It is preferable to contain a compound having a glycoluril skeleton (hereinafter also referred to as “reactive functional group-containing glycoluril compound”) as well as a “reactive functional group”.

The reactive functional group-containing glycoluril compound preferably has four or more reactive functional groups in one molecule from the viewpoint of the heat resistance of the cured product.

Examples of the reactive functional group in the reactive functional group-containing glycoluril compound include a thiol group, a carbon-carbon double bond, an epoxy group, a carboxyl group, and a hydroxyl group. Of these, a thiol group and / or a carbon-carbon double bond is preferable.
That is, the reactive functional group-containing glycoluril compound is included in the polythiol monomer when it has two or more thiol groups in one molecule as the reactive functional group, and carbon-carbon diene as the reactive functional group. When two or more heavy bonds are present in one molecule, they are included in the polyene monomer.

Specifically, the reactive functional group-containing glycoluril compound is preferably a compound represented by the following formula (1), a compound represented by the following formula (2-1), and the following formula (2-2). And at least one selected from the group consisting of a compound represented by the following formula (2-3) is more preferred.

In formula (1), R ¹ and R ² are hydrogen or a methyl group, and may be the same or different. X is a group containing a thiol group or a group containing a carbon-carbon double bond, and each X may be the same or different.

A preferable lower limit of the content of the reactive functional group-containing glycoluril compound in 100 parts by weight of the total polymerizable compound is 20 parts by weight, and a preferable upper limit is 90 parts by weight. When the content of the reactive functional group-containing glycoluril compound is within this range, the resulting sealant for a display element is more excellent in the effect of improving the reliability in a high-temperature and high-humidity environment. The minimum with more preferable content of the said reactive functional group containing glycoluril compound is 30 weight part, and a more preferable upper limit is 80 weight part.

The sealant for display elements of the present invention further contains, as the polymerizable compound, a thioether oligomer (hereinafter also simply referred to as “thioether oligomer”) formed by the reaction of the polythiol monomer and the polyene monomer. Is preferred.
The sealant for display element of the present invention contains the above thioether oligomer, so that the adhesiveness is improved, and the viscosity of the sealant for display element is moderately high so that unevenness does not easily occur during coating. It becomes.

The thioether oligomer is an addition polymerization reaction of the polythiol monomer and the polyene monomer in the range of 3: 1 to 1: 3 with respect to the polythiol monomer by light irradiation or heating in the presence of a polymerization initiator. Can be obtained as a polymer in the reaction mixture. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a thermal polymerization initiator is preferably used.
In addition, the said thioether oligomer may contain the unreacted thiol group and the unreacted carbon-carbon double bond, and does not need to contain the unreacted thiol group and the unreacted carbon-carbon double bond. That is, it may be a thioether oligomer that does not contain a thiol group or an unreacted carbon-carbon double bond obtained by sufficiently proceeding an addition polymerization reaction between the polythiol monomer and the polyene monomer. It may be a thioether oligomer containing an unreacted thiol group or an unreacted carbon-carbon double bond obtained by stopping the reaction in the middle.

The thermal polymerization initiator is not particularly limited, but a thermal radical polymerization initiator is preferably used.
As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile) and azobisisobutyronitrile.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
Moreover, as said photoinitiator, the thing similar to the photoinitiator mentioned as a polymerization initiator contained in the sealing agent for display elements of this invention mentioned later can be used.

In the addition polymerization reaction of the polythiol monomer and polyene monomer described above, the number of moles of thiol group of the polythiol monomer to the number of moles of carbon-carbon double bond of the polyene monomer (number of moles of thiol group / mol of carbon-carbon double bond When the number) is 0.15 or less, the polyene monomer usually remains as an unreacted component in the resulting reaction mixture.

In addition, the sealing agent for display elements of the present invention includes a polythiol monomer, a polyene monomer, and a thioether oligomer obtained by stopping the reaction during the addition polymerization reaction in the addition polymerization reaction of the polythiol monomer and the polyene monomer described above. What mixed the polymerization initiator, the phenol-type stabilizer, the carbodiimide compound, etc. in the mixture may be used.
The thioether oligomer may be prepared in advance with a polythiol monomer, a polyene monomer, or the like.
When the thioether oligomer is prepared in advance, the polythiol monomer and polyene monomer that are the raw materials of the thioether oligomer are the above-described tri- or higher-functional polythiol monomer and the tri-functional monomer contained in the display element sealing agent of the present invention. Each of the above polyene monomers may be the same or different.

The minimum with a preferable weight average molecular weight of the said thioether oligomer is 500, and a preferable upper limit is 40,000. When the weight average molecular weight of the thioether oligomer is within this range, the obtained sealant for display element is more excellent in the effect of suppressing the generation of outgas and the applicability. The more preferred lower limit of the weight average molecular weight of the thioether oligomer is 1500, the more preferred upper limit is 10,000, the still more preferred lower limit is 2000, and the more preferred upper limit is 8,000.
In the present specification, the “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). As a column used when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko KK) etc. are mentioned, for example.

The minimum with preferable content of the said thioether oligomer in 100 weight part of the said whole polymeric compound is 10 weight part, and a preferable upper limit is 70 weight part. When the content of the thioether oligomer is within this range, the obtained sealant for display element is more excellent in the effect of suppressing the generation of outgas and the coating property. The minimum with more preferable content of the said thioether oligomer is 20 weight part, and a more preferable upper limit is 60 weight part.

The sealant for display elements of the present invention contains a polymerization initiator.
As said polymerization initiator, a photoinitiator and the thermal polymerization initiator mentioned above are mentioned, A photoinitiator is used suitably.

The polymerization initiator has a preferred lower limit of molecular weight of 250 and a preferred upper limit of 1500. By using a polymerization initiator having a molecular weight of 250 to 1500, the sealant for display element of the present invention has excellent curability and has an excellent effect of suppressing the generation of outgas. Among these, from the viewpoint of reducing the generation of outgas, the more preferable lower limit of the molecular weight of the polymerization initiator is 300, the more preferable upper limit is 1050, the still more preferable lower limit is 348, and the further preferable upper limit is 790.

Examples of the photopolymerization initiator include a compound having an acylphosphine oxide skeleton, a compound having an α-aminoacetophenone skeleton, a compound having a benzyl ketal skeleton, a compound having an α-hydroxyacetophenone skeleton, a compound having a benzoin skeleton, and an oxime. Examples thereof include a compound having an ester skeleton, a compound having a titanocene skeleton, an organic peroxide, an azo compound, and an oligomer compound. These photopolymerization initiators may be used alone or in combination of two or more. Among them, from the viewpoint of photocurability, a compound having an acylphosphine oxide skeleton, a compound having an α-aminoacetophenone skeleton, a compound having a benzyl ketal skeleton, a compound having an α-hydroxyacetophenone skeleton, a compound having a benzoin skeleton, and an oxime It is preferably at least one selected from the group consisting of a compound having an ester skeleton, a compound having a titanocene skeleton, and an oligomer compound, a compound having an acylphosphine oxide skeleton, a compound having a benzyl ketal skeleton, and / or More preferably, it is an oligomer compound.
Here, the compound having an acylphosphine oxide skeleton means a compound in which a part of the acylphosphine oxide is substituted with another group. The compound having the α-aminoacetophenone skeleton means a compound in which a part of α-aminoacetophenone is substituted with another group. The compound having the benzyl ketal skeleton means a compound in which a part of α-dihydroxyacetophenone is substituted with another group. The compound having the α-hydroxyacetophenone skeleton means a compound in which a part other than the hydroxyl group of α-monohydroxyacetophenone is substituted with another group. The compound having the benzoin skeleton means a compound in which a part of benzoin is substituted with another group. The compound having an oxime ester skeleton means a compound in which a part of N-acetyldimethyloxime is substituted with another group. The compound having a titanocene skeleton means a compound in which a part of titanocene is substituted with another group. The organic peroxide means a compound having a peroxy group. The azo compound means a compound having an azo group.

Examples of the compound having an acylphosphine oxide skeleton include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, “LUCILIN TPO”), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ( BASF, “IRGACURE 819”) and the like.

Examples of the compound having an α-aminoacetophenone skeleton include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, “IRGACURE 907”), 2-benzyl. 2-Dimethylamino-1- (4-morpholinophenyl) butanone ("IRGACURE 369" manufactured by BASF), 1,2- (dimethylamino) -2-((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone (manufactured by BASF, “IRGACURE 379”) and the like.

Examples of the compound having the benzyl ketal skeleton include 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, “IRGACURE 651”).

Examples of the compound having an α-hydroxyacetophenone skeleton include 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl) -2-methyl-propane-1 -ON (manufactured by BASF, "IRGACURE 127"), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF, "IRGACURE 1173"), 1- (4- (2-hydroxy Ethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF, “IRGACURE 2959”) and the like.

Examples of the compound having an oxime ester skeleton include 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime) (manufactured by BASF Japan, “IRGACURE OXE01”), O -Acetyl-1- (6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethanone oxime (manufactured by BASF, “IRGACURE OXE02”) and the like.

Examples of the compound having a titanocene skeleton include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. (“BAGACURE 784” manufactured by BASF AG).

The oligomer compound mentioned as the photopolymerization initiator preferably has a degree of polymerization of 2 to 10 from the viewpoint of reducing the outgas generation, and moreover, it is difficult to generate outgas. It preferably has a binding functional group.
Specifically, for example, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propane) (manufactured by Lamberti, “ESACURE KIP 150”), polyethylene glycol 200-di (β -4 (4- (2-dimethylamino-2-benzyl) butanonylphenyl) piperazine) (IGM, “Omnipol 910”), (2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester (IGM “Omnipol TX”), (carboxymethoxymethoxybenzophenone)-(polyethylene glycol 250) diester (IGM, “Omnipol BP”) and the like.

The content of the polymerization initiator is preferably 0.1 parts by weight and preferably 5 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the polymerization initiator is within this range, a more uniform cured product can be obtained without reducing workability. The minimum with more preferable content of the said polymerization initiator is 0.5 weight part, and a more preferable upper limit is 4 weight part.

The sealant for display elements of the present invention may contain an adhesion promoter.
Examples of the adhesion-imparting agent include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and N- (aminoethyl) aminopropyltrimethoxy. Examples include silane coupling agents such as silane and mercaptopropyltrimethoxysilane, titanium coupling agents, and aluminum coupling agents. These adhesiveness imparting agents may be used alone or in combination of two or more.

The sealant for a display element of the present invention further includes a filler, a plasticizer, a surfactant, a flame retardant, an antistatic agent, an antifoaming agent, a leveling agent, and an ultraviolet absorber as long as the object of the present invention is not impaired. Etc. You may contain additives, such as.

Examples of the method for producing the sealant for display element of the present invention include, for example, a polythiol monomer, a polyene monomer, a polymerization initiator, a phenol-based stabilizer, a carbodiimide compound, and an adhesiveness imparting agent added as necessary. And the like are mixed uniformly using a stirrer.

The sealing agent for display elements of the present invention has a preferred lower limit of viscosity of 0.4 Pa · s and a preferred upper limit of 40 Pa · s measured using a cone rotor viscometer under the conditions of 20 ° C. and 20 rpm. When the viscosity is within this range, the obtained sealant for display element is more excellent in applicability. A more preferable lower limit of the viscosity is 1.0 Pa · s, and a more preferable upper limit is 6.0 Pa · s.

The sealing agent for display elements of the present invention preferably has an average visible light transmittance of 80% or more in a region of a cured product having a wavelength of 380 to 780 nm. When the average transmittance of visible light is 80% or more, it can be suitably used for applications requiring transparency. The average transmittance of the visible light is more preferably 95% or more.
In addition, the hardened | cured material which measures the average transmittance | permeability of the said visible light can be obtained by the method etc. which irradiate the ultraviolet-ray of 2000mJ / cm < ² > with respect to the sealing agent for display elements of this invention.

The sealant for a display element of the present invention preferably has a weight reduction rate of 0.15% or less when a 100 μm thick cured product is heated to 130 ° C. at a temperature rising rate of 10 ° C./min. Since the weight reduction rate can be regarded as an outgas generation amount, an adverse effect on the display element can be suppressed by being 0.15% or less. The weight reduction rate is more preferably 0.1% or less.
In addition, the hardened | cured material which measures the said weight decreasing rate can be obtained by the method etc. which irradiate 2000 mJ / cm < ² > of ultraviolet-rays with respect to the sealing agent for display elements of this invention apply | coated so that it may become thickness 100micrometer. it can.

The sealing agent for display elements of the present invention can be easily cured by light irradiation by using a photopolymerization initiator as the polymerization initiator.
Examples of the method of curing the sealant for display element of the present invention by light irradiation include a method of irradiating light with a wavelength of 300 to 400 nm and an accumulated light amount of 300 to 3000 mJ / cm ² .

Examples of the light source for irradiating the sealing agent for display element of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave excitation mercury lamp. , Metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used independently and 2 or more types may be used together.

Examples of light irradiation means for the sealant for display elements of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. Irradiation means may be used.

The sealant for display element of the present invention is a sealant for sealing the entire surface, front surface, rear surface, or periphery of the display element, or a seal for sealing an opening provided in the display element. It can be used as an agent, and is particularly preferably used for sealing the entire surface of the display element.
In the present specification, the above-mentioned “entire surface” does not necessarily mean 100% of the surface of the display element, but means the entire necessary sealing surface required for the display element. The “front surface” means a surface from which light is extracted, that is, a surface on the viewing side.

The sealing agent for display elements of this invention can be used for the sealing agent for organic EL display elements, the sealing agent for liquid crystal display elements, the sealing agent for electrochromic substrates, the sealing agent for electronic paper, etc., for example.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for display elements which can be excellent in adhesiveness and transparency, and can suppress the generation | occurrence | production of an outgas and gelatinization at the time of contacting with a metal can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Production of thioether oligomer)
50 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., “PEMP”) as a polythiol monomer and 50 parts by weight of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene monomer And 0.1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a thermal polymerization initiator using a stirrer (manufactured by Shinto Kagaku Co., “Three-One Motor HEIDON BLH300”) Mixing at 180 ° C. for 180 minutes gave a reaction mixture. The obtained reaction mixture was poured into a poor solvent, the precipitated oligomers were collected, and the solvent was removed under vacuum to obtain a thioether oligomer having a weight average molecular weight of 2000.

(Examples 1-12, Comparative Examples 1-4)
According to the mixing ratio described in Tables 1 and 2, each material was mixed using a stirrer (manufactured by Shinto Kagaku Co., Ltd., “Three-One Motor HEIDON BLH300”), and then heated at 80 ° C. for 10 minutes. Sealants for display elements of Examples 1 to 12 and Comparative Examples 1 to 4 were prepared.

<Evaluation>
About each sealing agent for display elements obtained by the Example and the comparative example, it evaluated by the following method. The results are shown in Tables 1 and 2.

(1) The sealants for display elements obtained in the low outgassing examples and comparative examples were applied at a rate of 100 mm / second using a slit coater so that the thickness after application was 50 μm, After irradiating ultraviolet rays of 2000 mJ / cm ² using an LED lamp with a wavelength of 365 nm, the film was formed by heating at 120 ° C. for 30 minutes.
Using a thermal analyzer (Seiko Instruments, “TG / DTA6200”), the weight loss rate when the film was heated to 130 ° C. at a temperature rising rate of 10 ° C./min was measured, and this was generated as outgas. The amount. “○” indicates that the outgas generation amount was less than 0.05%, “△” indicates that the outgas generation amount was 0.05% or more and less than 0.20%, and the outgas generation amount was 0.20% or more. The low outgassing property was evaluated as “×”.

(2) Curability After applying each transparent sealing agent for display elements obtained in Examples and Comparative Examples on a glass substrate and irradiating an ultraviolet ray of 2000 mJ / cm ² using an LED lamp with a wavelength of 365 nm, A film was formed by heating at 120 ° C. for 30 minutes. Then, the reaction rate was measured from the reduction rate of the peak derived from the carbon-carbon double bond by an analysis method using FT-IR. The curability was evaluated as “◯” when the reaction rate exceeded 90%, “Δ” when it exceeded 80% and 90% or less, and “X” when it was 80% or less.

(3) Adhesiveness 0.05 g of each sealant for display elements obtained in Examples and Comparative Examples was applied on a glass substrate using a micropipette. This substrate was bonded to another glass substrate on which a spacer was placed so as to have a thickness of 50 μm, irradiated with 2000 mJ / cm ² ultraviolet rays using an LED lamp with a wavelength of 365 nm, and then heated at 120 ° C. for 30 minutes. A sample for adhesion test was prepared. The obtained adhesion test sample was subjected to a peel test using EZ GRAPH (manufactured by Shimadzu Corporation) at a peel rate of 5 mm / min to measure the adhesive force. When the adhesive force is 1.0 N / cm or more, “◯”, when the adhesive force is 0.8 N / cm or more and less than 1.0 N / cm, “△”, and the adhesive force is 0.8 N / cm. The case where it was less than "x" evaluated adhesiveness.

(4) Anti-gelling property when contacted with metal 0.05 g of each sealant for display element obtained in Examples and Comparative Examples was applied on a stainless steel substrate using a micropipette. This substrate was bonded to another stainless steel substrate on which a spacer was disposed so as to have a thickness of 50 μm, and allowed to stand in an environment of 25 ° C. for 24 hours. The upper substrate was peeled off, the display element sealant on the substrate was wiped off with a waste cloth, and then the remaining wiping state on the substrate was observed. Evaluate the anti-gelation property when contacting a metal with "○" if no gel was seen, "△" if there was a slight gel, and "x" if the gel was entirely gelled. did.

(5) Display performance (5-1) Display performance of liquid crystal display element (production of liquid crystal display element)
Prepare two glass substrates (length 25mm, width 25mm, thickness 0.7mm) on which an ITO electrode with a thickness of 1000mm is formed on the surface and then an orientation film with a thickness of 800mm is applied on the surface by spin coating. Then, using a thermosetting epoxy resin (peripheral sealant) on one substrate, printing of a pattern in which a liquid crystal injection port was provided was performed by screen printing. Next, the substrate on which the pattern was printed was kept at 80 ° C. for 3 minutes to perform preliminary drying and fusion of the peripheral sealant to the substrate, and then returned to room temperature. Next, after spraying a spacer of 5 μm on the other substrate, the substrates are bonded together, and the peripheral sealant is cured for 2 hours with a hot press heated to 130 ° C. to cure the empty liquid crystal display element. Obtained. The obtained empty liquid crystal display element was vacuum-sucked, and then liquid crystal (“ZLI-4792”, manufactured by Merck & Co., Inc.) was injected from the injection port. After sealing with a stopper and irradiating an ultraviolet ray of 2000 mJ / cm ² using an LED lamp with a wavelength of 365 nm, it was heated at 120 ° C. for 30 minutes. Thereafter, the liquid crystal was annealed at 120 ° C. for 1 hour to produce a liquid crystal display element.

(Liquid crystal orientation disorder)
The obtained liquid crystal display element is exposed for 240 hours under conditions of 50 ° C. and 90% RH, and then driven in a halftone display state at a voltage of AC 3.5 V to polarize the liquid crystal alignment disorder near the inlet. Observed with a microscope. The case where no alignment disorder is confirmed is indicated by “◯”, the case where an alignment disorder less than 1 mm is confirmed is “Δ”, and the case where there is a clear alignment disorder (dark color unevenness) of 1 mm or more is indicated by “X”. The display performance of the liquid crystal display element was evaluated.

(5-2) Display performance of organic EL display element (production of a substrate on which a laminate including an organic light emitting material layer is disposed)
A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd., The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible in other different ways. 200 mg of tris (8-quinolinolato) aluminum (Alq ₃ ) was put in an unglazed crucible, and the inside of the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq ₃ was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. Then, after reducing the pressure in the vapor deposition unit of the vacuum vapor deposition apparatus to 2 × 10 ⁻⁴ Pa and depositing 5 μm of lithium fluoride at a deposition rate of 0.2 kg / s, deposit 1000 μm of aluminum at a rate of 20 kg / s. did. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate on which the laminate including the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.

(Coating with inorganic material film A)
A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminate of the substrate on which the laminate including the obtained organic light emitting material layer is disposed, and the inorganic material film A is formed by plasma CVD. Formed.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The thickness of the formed inorganic material film A of silicon nitride was about 0.2 μm.

(Formation of resin protective film)
On the inorganic material film A, each of the transparent sealing agents for display elements obtained in Examples and Comparative Examples is applied at a rate of 100 mm / sec using a slit coater so that the thickness after application becomes 50 μm. And applied. Next, an ultraviolet ray of 2000 mJ / cm ² was irradiated using an LED lamp having a wavelength of 365 nm, and then heated at 120 ° C. for 30 minutes to form a resin protective film.

(Coating with inorganic material film B)
A mask having a 12 mm × 12 mm opening was placed so as to cover the entire resin protective film, and an inorganic material film B was formed by plasma CVD to obtain a display element (organic EL display element).
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates of each are SiH ₄ gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The thickness of the formed inorganic material film B of silicon nitride was about 1 μm.

(Light emission state of organic EL display element)
The fabricated organic EL display elements were exposed for 240 hours under conditions of 85 ° C. and 85% RH, respectively, and then a voltage of 3 V was applied to visually observe the light emission state (light emission and dark spots, whether or not pixels were quenched). Organic light-emitting diode display with “◯” when there is no dark spot or peripheral quenching, “△” when dark spot or peripheral quenching is recognized, and “×” when non-light emitting part is significantly enlarged The display performance of the device was evaluated.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for display elements which can be excellent in adhesiveness and transparency, and can suppress the generation | occurrence | production of an outgas and gelatinization at the time of contacting with a metal can be provided.

Claims (9)

A polymerizable compound containing a polythiol monomer having three or more thiol groups in one molecule, a polyene monomer having three or more carbon-carbon double bonds in one molecule, a polymerization initiator, and a phenol-based compound A sealant for a display element, comprising a stabilizer and a carbodiimide compound. The sealant for a display element according to claim 1, wherein the phenol-based stabilizer is a hindered phenol-based stabilizer. 3. The sealant for a display element according to claim 1, wherein the content of the phenol-based stabilizer is 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the polymerizable compound. 4. The sealant for a display element according to claim 1, wherein the content of the carbodiimide compound is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the polymerizable compound. The polythiol monomer having three or more thiol groups in one molecule contains a polythiol monomer having a secondary thiol group. The sealing agent for a display element according to claim 1, 2, 3, or 4. 6. The display element seal according to claim 1, wherein the polythiol monomer having three or more thiol groups in one molecule has four or more thiol groups in one molecule. Stopper. The polyene monomer having three or more carbon-carbon double bonds in one molecule has four or more carbon-carbon double bonds in one molecule. 5. Sealant for display element according to 5 or 6. The polymerizable compound contains a reactive functional group capable of reacting with a polythiol monomer and / or a polyene monomer and a compound having a glycoluril skeleton, wherein the compound has a glycoluril skeleton. The sealing agent for display elements of description. The sealing agent for a display element according to claim 1, 2, 3, 4, 5, 6, 7 or 8, further comprising a thioether oligomer as the polymerizable compound.